Method of detecting leaks of fluoroolefin compositions and sensors used therefor

ABSTRACT

Disclosed are a method of detecting a leak of fluoroolefin compositions and sensors used therefor. In particular, the method is particularly useful for detecting a leak of a fluoroolefin refrigerant composition from a cooling system of an automotive vehicle. Such fluoroolefin refrigerant compositions have double bond structures which make them particularly well suited with sensing technologies, including: infrared sensors, UV sensors, NIR sensors, ion mobility or plasma chromatographs, gas chromatography, refractometry, mass spectroscopy, high temperature thick film sensors, thin film field effect sensors, pellistor sensors, Taguchi sensors and quartz microbalance sensors.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application claims the benefit of priority of U.S. ProvisionalApplication 60/844,869, filed Sep. 15, 2006.

FIELD OF THE INVENTION

This disclosure relates to a method of detecting a leak of fluoroolefincompositions and sensors used therefor. In particular, the disclosurerelates to detecting a leak of a fluoroolefin refrigerant compositionfrom a vapor compression system. Such refrigerant compositions may beuseful in cooling systems as replacements for existing refrigerants withhigher global warming potential.

BACKGROUND OF THE INVENTION

New environmental regulations on refrigerants have forced therefrigeration and air-conditioning industry to look for new refrigerantswith low global warming potential (GWP).

Replacement refrigerants are being sought that have low GWP, notoxicity, non-flammability, reasonable cost and excellent refrigerationperformance.

Fluoroolefins have been proposed as refrigerants alone or in mixtures.When used in a vapor compression system, any refrigerant has a tendencyto leak from the system over time, as holes develop in the system.However, the leakage of refrigerant is at times difficult to detect,especially where the holes in the system are small. A solution to thisproblem has been to add a dye to the refrigerant and let the dye runthrough the system. However, there is a cost associated with theaddition of the dye in terms of both materials and time. In addition,often the dye must be run through the system for a period of time beforethe leak can be detected, which requires follow up.

SUMMARY OF THE INVENTION

The method of the present invention eliminates the need for the use of adye to detect leaks in fluid systems. It provides nearly instantaneousfeedback for the location of a leak in the system, and eliminates the toexpense and time of adding a dye to the system. It is therefore morecost effective than known methods for detecting leaks.

The method of the present invention is based on the understanding of theunique double bond structure of fluoroolefins. Such double bondstructure allows the use of sensing technologies which have heretoforenot been available for detecting leaks.

Thus, in accordance with the present invention, there is provided amethod of detecting leaks of a fluoroolefin composition in a fluidsystem. The method comprises sensing the components of the system withsensing means for detecting leaks of a fluoroolefin composition. Inparticular, the sensing means is capable of detecting the double bondstructure in the fluoroolefin composition.

Also in accordance with the present invention, there is provided amethod for detecting a leak of a refrigerant fluid in a refrigeration orair-conditioning system wherein the refrigerant fluid comprises carbondioxide, said method comprising adding a fluoroolefin to saidrefrigerant fluid.

Further in accordance with the present invention, there is provided adetection system for detecting the double bond structure in afluoroolefin composition. Such detection system comprises means forsensing the double bond structure of the fluoroolefin composition. Thesensing means may comprise either a sensor which is used in-situ in thesystem, a wand tip which may be used proximate the components of thesystem, or an extraction device, which may be used remote from thecomponents of the system.

The sensor used in the sensing means of either embodiment may employ anyof the following technologies: infrared sensors, UV sensors. NIRsensors, ion mobility or plasma chromatographs, gas chromatography,refractometry, mass spectroscopy, high temperature thick film sensors,thin film field effect sensors, pellistor sensors, Taguchi sensors andquartz microbalance sensors.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of a refrigeration or air conditioningapparatus, including an extraction device which is used in accordancewith the method of the present invention.

FIG. 1A is a schematic diagram of an example of a wand tip which is usedin accordance with the method and the detection system of the presentinvention.

FIG. 2 shows the raw NIR spectral data for a sample of1,2,3,3,3-pentafluoropropene (HFC-1225ye).

FIG. 3 shows the background NIR spectrum acquired for the evacuatedsample cell as a blank.

FIG. 4 shows the background subtracted NIR spectrum for HFC-1225ye.

DESCRIPTION OF THE INVENTION

Provided in accordance with the present invention is a method ofdetecting a leak of a fluoroolefin composition from a fluid system. Thefluoroolefin compositions detected with the present invention have avariety of utilities, which include use as foaming agents, blowingagents, fire extinguishing agents, heat transfer mediums (such as heattransfer fluids and refrigerants for use in refrigeration systems,refrigerators, air conditioning systems, heat pumps, chillers, and thelike), to name a few. The type of fluid system from which a leak isdetected will depend on the utility of the composition. For instance,when the composition is a refrigerant, the fluid system from which aleak is detected may be a cooling system.

For exemplification, the present invention is illustrated with respectto cooling system of an automotive vehicle. Such a system is showngenerally at 10 in FIG. 1. Such a cooling system may be avapor-compression system. A vapor compression system is a closed loopsystem which re-uses refrigerant in multiple steps producing a coolingeffect in one step and a heating effect in a different step. Such asystem generally includes an evaporator, a compressor, a condenser andan expansion device, as will be described below in detail with respectto FIG. 1. The vapor compression system may be used in either stationaryor mobile refrigeration or air-conditioning applications.

With reference to FIG. 1, gaseous refrigerant from an evaporator 42flows through a hose 63 to the inlet of a compressor 12, and is thendischarged. Various types of compressors may be used with the presentinvention, including reciprocating, rotary jet, centrifugal, scroll,screw or axial-flow, depending on the mechanical means to compress thefluid, or as positive-displacement (e.g., reciprocating, scroll orscrew) or dynamic (e.g., centrifugal or jet).

The compressed refrigerant gas from the compressor flows through thecompressor outlet and through a hose 61 to a condenser 41. A pressureregulating valve 51 in hose 61 may be used. This valve allows recycle ofthe refrigerant flow back to the compressor via a hose 63, therebyproviding the ability to control the pressure of the refrigerantreaching the condenser 41 and if necessary to prevent compressor surge.The compressed refrigerant is condensed in the condenser, thus givingoff heat. The liquid refrigerant flows through an expansion device 52via a hose 62 to the evaporator 42, which is located in for instance,the passenger compartment of an automobile, or in the vicinity ofanother location to be cooled. In the evaporator, the liquid refrigerantis vaporized, providing cooling and the cycle then repeats. Theexpansion device 52 may be an expansion valve, a capillary tube or anorifice tube.

Further in accordance with the present invention, there is provided adetection system for detecting the double bond structure in afluoroolefin composition. Such detection system comprises means forsensing the double bond structure of the fluoroolefin composition. Thesensing means may include a sensor which is used in-situ in the system.Alternatively, the sensing means may include an extraction device, showngenerally at 70 in FIG. 1. A sensor 72 is placed inside the extractiondevice. A line 74 brings the fluid to be sensed to the extractiondevice. Alternatively, in another embodiment, the sensing means maycomprise a wand tip, as shown at 70′ in FIG. 1A. A sensor 72′ isincluded in this hand-held device. This wand tip is generally a handheld device, which may be placed near the fluid in order to detect theleak. An advantage of this type of detector is rapid response so theoperator immediately detects a leak as a “wand” tip passes over aleakage site. The particular device as shown in FIG. 1A is a handheldrefractometer for observing liquid samples at atmospheric pressure.However, it should be understood that the present invention is notlimited to observing liquid samples, but may also include hand helddevices for detecting gases, such as, for example, a hand held gaschromatograph.

The sensor used in the sensing means of either embodiment may employ anyof the following technologies: infrared sensors, UV sensors, NIRsensors, ion mobility or plasma chromatographs, gas chromatography,refractometry, mass spectroscopy, high temperature thick film sensors,thin film field effect sensors, pellistor sensors, Taguchi sensors andquartz microbalance sensors. Such technologies are known in the art.

Infrared sensors of the present invention make use of unique spectralabsorbance in the infrared region for all polyatomic gases. Bymeasurement of the spectral intensities in regions specifically selectedfor a target analyte gas, the concentration of that gas can bedetermined.

There are many techniques available for selecting the spectral regiondetected including optical filters, spectrographs, transform techniquessuch as Fourier and Hadamard, emission sources with restricted emissionranges, detectors with specific sensitivities including microphonesenclosed with the analyte gas. The application of infrared spectroscopyto gas detection and concentration determination is well known tospectroscopists.

As used herein, UV/vis means “ultraviolet and visible regions of thelight spectrum”. A UV/vis spectrophotometer measures the intensity oflight passing through a sample (I), and compares it to the intensity oflight before it passes through the sample (I_(o)). The ratio I/I_(o) iscalled the transmittance, and is usually expressed as a percentage (%T). The absorbance, A, is based on the transmittance:A=−log(% T)

The basic parts of a spectrophotometer are a light source (often anincandescent bulb for the visible wavelengths, or a deuterium arc lampin the ultraviolet), a holder for the sample, a diffraction grating ormonochromator to separate the different wavelengths of light, and adetector. The detector is typically a photodiode or a charge-coupleddevice which can store patterns of charge, also known as a CCD.Photodiodes are used with monochromators, which filter the light so thatonly light of a single wavelength reaches the detector. Diffractiongratings are used with CCDs, which collect light of differentwavelengths on different pixels.

As used herein, NIR means “near infrared light spectrum”. Near infraredspectrometer (NIRS) is a spectroscopic method utilizing the nearinfra-red region of the electromagnetic spectrum (from about 800 nm to2500 nm). NIRS is based on molecular overtone and combinationvibrations. The molar absorptivity in the near IR region is typicallyquite small.

Instrumentation for near-IR spectroscopy is similar to instruments forthe visible and mid-IR ranges. There is a source, a detector, and adispersive element (such as a prism, or more commonly a diffractiongrating) to allow the intensity at different wavelengths to be recorded.Fourier transform instruments using an interferometer are also useful,especially for wavelengths above ˜1000 nm. Depending on the sample, thespectrum can be measured in transmission or in reflection.

Common incandescent or quartz halogen light bulbs are most often used asbroadband sources of near infrared radiation for analyticalapplications. Light-emitting diodes (LEDs) are also used. The type ofdetector used depends primarily on the range of wavelengths to bemeasured. Silicon-based CCDs, InGaAs and PbS devices are suitable.

Ion mobility spectrometry is based upon two principles: (1) theionization of sample molecules through gas phase chemical reactions bythe transfer of an electron or a proton, and (2) the characterization ofthese ions based upon gas phase mobility in a weak electric field. Themass, size, and shape of these ions will govern the mobility through avoltage gradient, and this can be measured as time required to traversea fixed distance. Thus IMS detectors yield a drift time or mobilityvalue which is characteristic of certain ions (i.e., chemicals) andprovide specificity of response (for example leak detection). Theinitial step of ion formation is common to all ion mobilityspectrometers. In order to achieve this, sample molecules must in someway be transported from a suspected item into the IMS instrument. Thisis usually accomplished by using a gas pump to sample the air for thesuspected leak. Leak detection can be relatively remote from theinstrument using a hose (stainless steel or various plastics or rubber)combined with the air-sampling pump. Simultaneous detection of multiplegasses has been demonstrated at the ppm to ppb levels. The ambient aircontains a particular reactant ion peak and hydrofluoric acid (HF). Thedetection by drift time discrimination is shown on the plot of collectorcurrent versus drift time. This is a very powerful technique to quicklyand unambiguously detect both amounts and composition of the ambientair.

As used herein, GC means is a “gas chromatograph or gas chromatographicanalytical technique”. Fluids, and refrigerants in particular, can beidentified by Micro GC detectors that are ion detectors with varyingmethods of ionizing the components eluting from the GC's column. An iondetector is analogous to a capacitor or vacuum tube. It can beenvisioned as two metal grids separated by air with inverse chargesplaced on them. An electric potential difference (voltage) existsbetween the two grids. After components are ionized in the detector,they enter the region between the two grids, causing current to passfrom one to the other. This current is amplified and is the signalgenerated by the detector, The higher the concentration of thecomponent, the more ions are generated, and the greater the current.

A flame ionization detector (FID) uses an air-hydrogen flame to produceions. As components elute from the GC's column they pass through theflame and are burned, producing ions. The ions produce an electriccurrent, which is the signal output of the detector.

A Thermal Conductivity Detector (TCD) consists of an electrically-heatedwire or thermistor. The temperature of the sensing element depends onthe thermal conductivity of the gas flowing around it. Changes inthermal conductivity, such as when organic molecules displace some ofthe carrier gas, cause a temperature rise in the element, which issensed as a change in resistance.

The Electron Capture Detector (ECD) uses a radioactive Beta particle(electrons) emitter—a typical source contains a metal foil holding 10millicuries of Nickel-63. The electrons formed are attracted to apositively charged anode, generating a steady current. As the sample iscarried into the detector by a stream of nitrogen or a 5% methane, 95%argon mixture, analyte molecules capture the electrons and reduce thecurrent between the collector anode and a cathode. The analyteconcentration is thus proportional to the degree of electron capture,and this detector is particularly sensitive to halogens, organometalliccompounds, nitriles, or nitro compounds.

The ECD is sensitive with the detection limit of 5 femtograms per second(fg/s), and the detector commonly exhibits a 10,000-fold linear range.This makes it possible to detect the specific halogenated compounds evenat levels of only one part per trillion (ppt).

A Photo-Ionization Detector (PID) is an ion detector which useshigh-energy photons, typically in the UV range, to produce ions. Ascomponents elute from the GC's column they are bombarded by high-energyphotons and are ionized. The ions produce an electric current, which isthe signal output of the detector. The greater the concentration of thecomponent, the more ions are produced, and the greater the current.

Refractometry uses the Refractive Index of fluids, such as refrigerants,in the liquid state to identify refrigerants in a leak scenario or todetermine the composition in a blend so as to adjust to a desiredcomposition. Refractive Index is defined as the angular change in a beamof light passing through the interface of two different substances. Thetechnique uses the fact that each refrigerant has a different atomiccomposition and therefore a different Refractive Index at a giventemperature. Since the Refractive Index is nearly linear with respect ofany two components in the mixture, fairly accurate estimates of two orthree component mixtures can be made.

A refractometer is used to determine the refractive index of a substanceor some physical property of a substance that is directly related to itsrefractive index. A sample of fluid is introduced into a sample chamberand a source of light is passed through the interface of the fluid and awindow in the chamber. The refractometer sensor determines the angle oflight emerging from the refrigerant fluid. The fluid is identified byreference to known, pre-determined relationship data for a plurality ofdifferent fluids. In a more advanced sensor, the temperature can bevaried to obtain data, to identify the constituents of multi-partmixtures of certain fluids and measure the percentage of the mixtures.Certain types of refractometers can be used for measuring gases andliquids.

A traditional handheld refractometer works on the critical angleprinciple. They utilize lenses and prisms to project a shadow line ontoa small glass reticle inside the instrument, which is then viewed by theuser through a magnifying eyepiece. In use, a sample is sandwichedbetween a measuring prism and a small cover plate. Light travelingthrough the sample is either passed through to the reticle or totallyinternally reflected. The net effect is that a shadow line is formedbetween the illuminated area and the dark area. It is at the point thatthis shadow line crosses the scale that a reading is taken. Becauserefractive index is very temperature to dependent, it is important touse a refractometer with automatic temperature compensation.Compensation is accomplished through the use of a small bi-metal stripthat moves a lens or prism in response to temperature changes.

A mass spectrometer is a device that measures the mass-to-charge ratioof ions. This is achieved by ionizing the sample and separating ions ofdiffering masses and recording their relative abundance by measuringintensities of ion flux. A typical mass spectrometer comprises threeparts: an ion source, a mass analyzer, and a detector system. Each gasmixture will display a unique spectrum that can be directly related tothe composition and concentration of the refrigerant mixture.

The fragmentation patterns of fluoroolefins are unique among fluids,such as other refrigerants and most other environmental gases allowingit to be specifically identified and its concentration determinedrelative to other gases present. The fragmentation pattern should bedifferent enough from other gases present near an internal combustionengine such as an automobile engine that it will be easilydifferentiated by this method. Furthermore, sensing techniques such asmass spectroscopy provide the option of measuring the concentration ofother gases that might be present as well.

In another embodiment high temperature, thick film sensors may functionas sensors for the present inventive method. Many semi-conductingmaterials become significantly conductive at higher temperatures, e.g.,at temperatures above 400° C. These materials become conductive becausevalence electrons are excited to conduction bands due to their thermalenergy. Gases that can either donate or receive electrons from thevalence bands change the population of electrons in the conduction bandsand thereby the materials conductivity.

Chemical selectivity of high temperature, thick film, sensors isachieved by changing the primary constituent itself and doping the film.In order to impart selectivity to this technique, arrays of sensorscontaining different primary constituents and/or dopants are employed,and the relationship of the concentration of any given gas to the outputof each array-sensing element is determined empirically.

In another embodiment, thin film, field effect sensors may function assensors for the present inventive method. Field effect sensors are basedon the field effect generated by gases in metal oxide semiconductorfield-effect transistor (MOSFET) devices with catalytic metals. Thecharging of the gate contact by the gas molecules results in a voltagechange in the sensor signal. The choice of operation temperature, gatemetal, and structure of the gate metal determine the selectivity of thegas response. For devices based on silicon (Si) as the semiconductor,Si-MOSFET, the operation temperature is 150-200° C. For devices based onsilicon carbide as the semiconductor, SiC-MOSFET, the operationtemperature is 200-600° C.

The selectivity and sensitivity of MOSFET sensors is achieved bymodification of the semiconductor, its doping, and the temperature atwhich the device is operated.

In another embodiment, pellistor catalytic gas sensors may be used assensors in the present inventive method. The pellistor is a miniaturecalorimeter used to measure the energy liberated on oxidation of a gas.It consists of a coil of small diameter platinum wire supported in arefractory bead. The coil is used to heat the bead electrically to itsoperating temperature (about 500° C.) and to detect changes intemperature produced by the oxidation of the gas. Selectivity ofpellistor sensors is achieved by modification of the composition of therefractory bead.

In another embodiment, Taguchi sensors may be used as sensors in thepresent inventive method. Taguchi sensors are composed of powders madeof semiconducting metal oxides. When a metal oxide crystal such as SnO₂is heated at a certain high temperature in air, oxygen is adsorbed onthe crystal surface with a negative charge. Then donor electrons in thecrystal surface are transferred to the adsorbed oxygen, resulting inleaving positive charges in a space charge layer. Thus, surfacepotential is formed to serve as a potential barrier against electronflow. Inside the sensor, electric current flows through the conjunctionparts (grain boundary) of SnO₂ micro crystals. At grain boundaries,adsorbed oxygen forms a potential barrier that prevents carriers frommoving freely. The electrical resistance of the sensor is attributed tothis potential barrier.

In the presence of gases capable of removing oxygen from the surface athigh temperature, the surface density of the negatively charged oxygendecreases, so the barrier height in the grain boundary is reduced. Thereduced barrier height decreases sensor resistance.

The selectivity and sensitivity of Taguchi sensors can be modifiedthrough selection of the metal oxides, oxide doping, and othermodifications of the oxide surface along with the temperature ofoperation.

In another embodiment, Quartz Microbalance Sensors may be used assensors in the present inventive method. Quartz microbalance sensortechnology is based on measuring the frequency of polymer-coated quartzcrystals. The frequency is influenced by bulk absorption of analytemolecules into the polymer matrix. The sensitivity and selectivity ofthe microbalance sensors can be varied through the selection ofdifferent polymer coatings, having different functional groups in theside chains. Bulk absorption of analyte molecules into the polymer layerincreases the mass of the quartz crystal, resulting in a decrease of theresonance frequency. The absorption process is fully reversible. Resinssuch as those sold under the trademark Nafion® by E. I. du Pont deNemours and Company of Wilmington, Del., PTFE, and polystyrenesulfonates are used to tailor the sensor response to specific analytesincluding refrigerant gases.

These sensing technologies have been found to be particularly useful indetermining the components of fluoroolefin compositions, which havedouble bonds. Representative fluoroolefins include but are not limitedto all compounds as listed in Table 1 and Table 2. As can be seen fromthese Tables, the fluoroolefins have at least one double bond.Fluoroolefins, as used herein, comprise compounds with 2 to 12 carbonatoms, in another embodiment 3 to 10 carbon atoms, and in yet anotherembodiment 3 to 7 carbon atoms.

In one embodiment of the invention fluoroolefins may be compounds (andmixtures of such compounds) having the formula E— or Z—R¹CH═CHR²(Formula I), wherein R¹ and R² are, independently, C₁ to C₆perfluoroalkyl groups. Examples of R¹ and R² groups include, but are notlimited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂, CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃,CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅,CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₂C₂F₅, and C(CF₃)₂CF₂C₂F₅. Exemplary,non-limiting Formula I compounds are presented in Table 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iECF₃CH═CHCF₂CF—(CF₃)₂1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene F14sECF₃CH═CHCF(CF₃)—C₂F₅1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene F14tECF₃CH═CHC(CF₃)₃1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23EC₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iEC₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-eneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tECF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2-ene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-eneF24iE C₂F₅CH═CHCF₂CF—(CF₃)₂1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene F24sEC₂F₅CH═CHCF(CF₃)—C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept-3-ene F24tEC₂F₅CH═CHC(CF₃)₃1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene F33EC₂F₅CF₂CH═CH—CF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE(CF₃)₂CFCH═CH—CF(CF₃)₂1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene F33iEC₂F₅CF₂CH═CH—CF(CF₃)₂1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene F16ECF₃CH═CH(CF₂)₅CF₃1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene F16sECF₃CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2- eneF16tE CF₃CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25EC₂F₅CH═CH(CF₂)₄CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iEC₂F₅CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3- eneF25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3-ene F34EC₂F₅CF₂CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iEC₂F₅CF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4- eneF34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)oct-4- eneF34tE C₂F₅CF₂CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene F3i4E(CF₃)₂CFCH═CH—(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3- eneF3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene F3i4sE(CF₃)₂CFCH═CH—CF(CF₃)C₂F₅1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3-ene F3i4tE(CF₃)₂CFCH═CH—C(CF₃)₃1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-ene F26EC₂F₅CH═CH(CF₂)₅CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene F26sEC₂F₅CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene F26tE C₂F₅CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)oct- 3-eneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene F35iEC₂F₅CF₂CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-ene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)oct- 4-eneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene F3i5iE (CF₃)₂CFCH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct- 3-eneF3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene F44ECF₃(CF₂)₃CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec-5-ene F44iECF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene F44sE CF₃(CF₂)₃CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene F44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-bis(trifluoromethyl)oct- 3-eneF4i4iE (CF₃)₂CFCF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct- 4-eneF4i4sE (CF₃)₂CFCF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)oct- 4-eneF4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-eneF4s4sE C₂F₅CF(CF₃)CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct- 4-eneF4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-eneF4t4tE (CF₃)₃CCH═CH—C(CF₃)₃1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹I with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂. This contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include fabricated from stainlesssteels, in particular of the austenitic type, and the well-known highnickel alloys such as nickel-copper alloys, sold under the trademarkMonel®, nickel based alloys, Hastelloy®, and nickel-chromium alloys,sold under the trademark Inconel®.

Alternatively, the reaction may take be conducted in semi-batch mode inwhich the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature. The ratio of perfluoroalkyliodide to perfluoroalkyltrihydroolefin should be between about 1:1 toabout 4:1, preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1tend to result in large amounts of the 2:1 adduct as reported byJeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4, pages261-270 (1974).

In some embodiments, temperatures for contacting of said perfluoroalkyliodide with said perfluoroalkyltrihydroolefin are preferably within therange of about 150° C. to 300° C., preferably from about 170° C. toabout 250° C., and most preferably from about 180° C. to about 230° C.Suitable contact times for the reaction of the perfluoroalkyl iodidewith the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or in some embodiments berecovered and purified by distillation prior to the dehydroiodinationstep.

In some embodiments, the dehydroiodination step is carried out bycontacting the trihydroiodoperfluoroalkane with a basic substance.Suitable basic substances include alkali metal hydroxides (e.g., sodiumhydroxide or potassium hydroxide), alkali metal oxide (for example,sodium oxide), alkaline earth metal hydroxides (e.g., calciumhydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkalimetal alkoxides (e.g. sodium methoxide or sodium ethoxide), aqueousammonia, sodium amide, or mixtures of basic substances such as sodalime. Preferred basic substances are sodium hydroxide and potassiumhydroxide. Said contacting of the trihydroiodoperfluoroalkane with abasic substance may take place in the liquid phase preferably in thepresence of a solvent capable of dissolving at least a portion of bothreactants. Solvents suitable for the dehydroiodination step include oneor more polar organic solvents such as alcohols (e.g., methanol,ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiarybutanol), nitrites (e.g., acetonitrile, propionitrile, butyronitrile,benzonitrile, or adiponitrile), dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choiceof solvent may depend on the boiling point product and the ease ofseparation of traces of the solvent from the product duringpurification. Typically, ethanol or isopropanol are good solvents forthe reaction.

In some embodiments, the dehydroiodination reaction may be carried outby addition of one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction may be fabricated from glass, ceramic, ormetal and is preferably agitated with an impeller or stirring mechanism.

In certain embodiments, the temperatures suitable for thedehydroiodination reaction are from about 10° C. to about 100° C.,preferably from about 20° C. to about 70° C. In other embodiments, thedehydroiodination reaction may be carried out at ambient pressure or atreduced or elevated pressure. In certain embodiments, dehydroiodinationreactions is one in which the compounds of Formula I is distilled out ofthe reaction vessel as it is formed.

In alternative embodiments, the dehydroiodination reaction may beconducted by contacting an aqueous solution of said basic substance witha solution of the trihydroiodoperfluoroalkane in one or more organicsolvents of lower polarity such as an alkane (e.g., hexane, heptane, oroctane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon(e.g., methylene chloride, chloroform, carbon tetrachloride, orperchloroethylene), or ether (e.g., diethyl ether, methyl tert-butylether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane,dimethoxyethane, diglyme, or tetraglyme) in the presence of a phasetransfer catalyst. Suitable phase transfer catalysts include quaternaryammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammoniumhydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammoniumchloride, and tricaprylylmethylammonium chloride), quaternaryphosphonium halides (e.g., triphenylmethylphosphonium bromide andtetraphenylphosphonium chloride), or cyclic polyether compounds known inthe art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Acccording to alternative embodiments, the dehydroiodination reactionmay be conducted in the absence of solvent by adding thetrihydroiodoperfluoroalkane to a solid or liquid basic substance.

In some embodiments, suitable reaction times for the dehydroiodinationreactions are from about 15 minutes to about six hours or more dependingon the solubility of the reactants. In some embodiments, thedehydroiodination reaction is rapid and requires about 30 minutes toabout three hours for completion.

The compound of Formula I may be recovered from the dehydroiodinationreaction mixture by phase separation after addition of water, bydistillation, or by a combination thereof.

The compositions in some embodiments may comprise a single compound ofFormula I, for example, one of the compounds in Table 1, or may comprisea combination of compounds of Formula I.

In another embodiment, fluoroolefins may be compounds as presented inTable 2 (including mixtures thereof. The compositions in some embodimentmay comprise a single compound in Table 2, or may comprise a combinationof compounds of Table 2, that is, a mixture thereof.

TABLE 2 Code Structure Chemical name HFC-1225ye CF₃CF═CHF1,2,3,3,3-pentafluoro-1-propene HFC-1225zc CF₃CH═CF₂1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF₂CF═CF₂1,1,2,3,3-pentafluoro-1-propene HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF₃CF═CH₂2,3,3,3,-tetrafluoro-1-propene HFC-1234ze CF₃CH═CHF1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH₂FCF═CF₂1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF₂CH═CF₂1,1,3,3-tetrafluoro-1-propene HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1243yf CHF₂CF═CH₂2,3,3-trifluoro-1-propene HFC-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propeneHFC-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFC-1243zc CH₂FCH═CF₂1,1,3-trifluoro-1-propene HFC-1243ye CHF₂CF═CHF1,2,3-trifluoro-1-propene HFC-1243ze CHF₂CH═CHF1,3,3-trifluoro-1-propene FC-1318my CF₃CF═CFCF₃1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF₃CF₂CF═CF₂1,1,2,3,3,4,4,4-octafluoro-1-butene HFC-1327my CF₃CF═CHCF₃1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF═CFCF₂CF₃1,2,3,3,4,4,4-heptafluoro-1-butene HFC-1327py CHF₂CF═CFCF₃1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF₃)₂C═CHF1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1- propene HFC-1327czCF₂═CHCF₂CF₃ 1,1,3,3,4,4,4-heptafluoro-1-butene HFC-1327cye CF₂═CFCHFCF₃1,1,2,3,4,4,4-heptafluoro-1-butene HFC-1327cyc CF₂═CFCF₂CHF₂1,1,2,3,3,4,4-heptafluoro-1-butene HFC-1336yf CF₃CF₂CF═CH₂2,3,3,4,4,4-hexafluoro-1-butene HFC-1336mzz CF₃CH═CHCF₃1,1,1,4,4,4-hexafluoro-2-butene HFC-1336ze CHF═CHCF₂CF₃1,3,3,4,4,4-hexafluoro-1-butene HFC-1336eye CHF═CFCHFCF₃1,2,3,4,4,4-hexafluoro-1-butene HFC-1336eyc CHF═CFCF₂CHF₂1,2,3,3,4,4-hexafluoro-1-butene HFC-1336pyy CHF₂CF═CFCHF₂1,1,2,3,4,4-hexafluoro-2-butene HFC-1336qy CH₂FCF═CFCF₃1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF₂CH═CFCF₃1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF₃CH═CFCHF₂1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF₂═CFCF₂CH₂F1,1,2,3,3,4-hexafluoro-1-butene HFC-1336pe CF₂═CFCHFCHF₂1,1,2,3,4,4-hexafluoro-1-butene HFC-1336ft CH₂═C(CF₃)₂3,3,3-trifluoro-2-(trifluoromethyl)-1-propene HFC-1345qz CH₂FCH═CFCF₃1,1,1,2,4-pentafluoro-2-butene HFC-1345mzy CF₃CH═CFCH₂F1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF₃CF₂CH═CH₂3,3,4,4,4-pentafluoro-1-butene HFC-1345mzz CHF₂CH═CHCF₃1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH₃CF═CFCF₃1,1,1,2,3-pentafluoro-2-butene HFC-1345fyc CH₂═CFCF₂CHF₂2,3,3,4,4-pentafluoro-1-butene HFC-1345pyz CHF₂CF═CHCHF₂1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH₃CF₂CF═CF₂1,1,2,3,3-pentafluoro-1-butene HFC-1345pyy CH₂FCF═CFCHF₂1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH₂FCF₂CF═CF₂1,2,3,3,4-pentafluoro-1-butene HFC-1345ctm CF₂═C(CF₃)(CH₃)1,1,3,3,3-pentafluoro-2-methyl-1-propene HFC-1345ftp CH₂═C(CHF₂)(CF₃)2-(difluoromethyl)-3,3,3-trifluoro-1-propene HFC-1354fzc CH₂═CHCF₂CHF₂3,3,4,4-tetrafluoro-1-butene HFC-1354ctp CF₂═C(CHF₂)(CH₃)1,1,3,3-tetrafluoro-2-methyl-1-propene HFC-1354etm CHF═C(CF₃)(CH₃)1,3,3,3-tetrafluoro-2-methyl-1-propene HFC-1354tfp CH₂═C(CHF₂)₂2-(difluoromethyl)-3,3-difluoro-1-propene HFC-1354my CF₃CF═CFCH₃1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH₃CF═CHCF₃1,1,1,3-tetrafluoro-2-butene FC-141-10myy CF₃CF═CFCF₂CF₃1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene FC-141-10cy CF₂═CFCF₂CF₂CF₃1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene HFC-1429mzt (CF₃)₂C═CHCF₃1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2- butene HFC-1429myzCF₃CF═CHCF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene HFC-1429mzyCF₃CH═CFCF₂CF₃ 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene HFC-1429eycCHF═CFCF₂CF₂CF₃ 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene HFC-1429czcCF₂═CHCF₂CF₂CF₃ 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene HFC-1429cyccCF₂═CFCF₂CF₂CHF₂ 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene HFC-1429pyyCHF₂CF═CFCF₂CF₃ 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene HFC-1429myycCF₃CF═CFCF₂CHF₂ 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene HFC-1429myyeCF₃CF═CFCHFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene HFC-1429eyymCHF═CFCF(CF₃)₂ 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)- buteneHFC-1429cyzm CF₂═CFCH(CF₃)₂1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1- butene HFC-1429mztCF₃CH═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-3-(trifluoromethyl)-2- buteneHFC-1429czym CF₂═CHCF(CF₃)₂1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1- butene HFC-1438fyCH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1-pentene HFC-1438eyccCHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1-pentene HFC-1438ftmcCH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1- buteneHFC-1438czzm CF₂═CHCH(CF₃)₂ 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1butene HFC-1438ezym CHF═CHCF(CF₃)₂1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1- butene HFC-1438ctmfCF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2-(trrifluoromethyl)-1- buteneHFC-1438mzz CF₃CH═CHCF₂CF₃ 1,1,1,4,4,5,5,5-octafluoro-2-penteneHFC-1447fzy (CF₃)₂CFCH═CH₂ 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFC-1447fz CF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1-penteneHFC-1447fycc CH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1-penteneHFC-1447czcf CF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1-penteneHFC-1447mytm CF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene HFC-1447fyz CH₂═CFCH(CF₃)₂2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1- butene HFC-1447ezzCHF═CHCH(CF₃)₂ 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1- buteneHFC-1447qzt CH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butene HFC-1447syt CH₃CF═C(CF₃)₂2,4,4,4-tetrafluoro-3-(trifluoromethyl)-2- butene HFC-1456szt(CF₃)₂C═CHCH₃ 3-(trifluoromethyl)-4,4,4-trifluoro-2-butene HFC-1456szyCF₃CF₂CF═CHCH₃ 3,4,4,5,5,5-hexafluoro-2-pentene HFC-1456mstzCF₃C(CH₃)═CHCF₃ 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene HFC-1456fzceCH₂═CHCF₂CHFCF₃ 3,3,4,5,5,5-hexafluoro-1-pentene HFC-1456ftmfCH₂═C(CF₃)CH₂CF₃ 4,4,4-trifluoro-2-(trifluoromethyl)-1-butene FC-151-12cCF₃(CF₂)₃CF═CF₂ 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1- hexene (orperfluoro-1-hexene) FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3- hexene (or perfluoro-3-hexene)FC-151-12mmtt (CF₃)₂C═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene FC-151-12mmzz (CF₃)₂CFCF═CFCF₃1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl)-2-penteneHFC-152-11mmtz (CF₃)₂C═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene HFC-152-11mmyyz (CF₃)₂CFCF═CHCF₃1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-penteneHFC-153-10mmyzz CF₃CH═CHCF(CF₃)₂ 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene HFC-153-10mzz CF₃CH═CHCF₂CF₂CF₃1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene HFC-153-10mczz CF₃CF₂CH═CHCF₂CF₃1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene PFBE CF₃CF₂CF₂CF₂CH═CH₂3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (or (or HFC-1549fz)perfluorobutylethylene) HFC-1549fztmm CH₂═CHC(CF₃)₃4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1- butene HFC-1549mmtts(CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene HFC-1549fycz CH₂═CFCF₂CH(CF₃)₂2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1- pentene HFC-1549mytsCF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl2- penteneHFC-1549mzzz CF₃CH═CHCH(CF₃)₂1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2- pentene HFC-1558szyCF₃CF₂CF₂CF═CHCH₃ 3,4,4,5,5,6,6,6-octafluoro-2-hexene HFC-1558fzcccCH₂═CHCF₂CF₂CF₂CHF₂ 3,3,4,4,5,5,6,6-octafluoro-2-hexene HFC-1558mmtzc(CF₃)₂C═CHCF₂CH₃ 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2- penteneHFC-1558ftmf CH₂═C(CF₃)CH₂C₂F₅4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1- pentene HFC-1567ftsCF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2-methyl-1- penteneHFC-1567szz CF₃CF₂CF₂CH═CHCH₃ 4,4,5,5,6,6,6-heptafluoro-2-hexeneHFC-1567fzfc CH₂═CHCH₂CF₂C₂F₅ 4,4,5,5,6,6,6-heptafluoro-1-hexeneHFC-1567sfyy CF₃CF₂CF═CFC₂H₅ 1,1,1,2,2,3,4-heptafluoro-3-hexeneHFC-1567fzfy CH₂═CHCH₂CF(CF₃)₂4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1- pentene HFC-1567myzzmCF₃CF═CHCH(CF₃)(CH₃) 1,1,1,2,5,5,5-heptafluoro-4-methyl-2- penteneHFC-1567mmtyf (CF₃)₂C═CFC₂H₅ 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene FC-161-14myy CF₃CF═CFCF₂CF₂C₂F₅1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro- 2-heptene FC-161-14mcyyCF₃CF₂CF═CFCF₂C₂F₅ 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene HFC-162-13mzy CF₃CH═CFCF₂CF₂C₂F₅1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2- heptene HFC162-13myzCF₃CF═CHCF₂CF₂C₂F₅ 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2- hepteneHFC-162-13mczy CF₃CF₂CH═CFCF₂C₂F₅1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3- heptene HFC-162-13mcyzCF₃CF₂CF═CHCF₂C₂F₅ 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3- hepteneHFC-C1316cc cyclo-CF₂CF₂CF═CF— 1,2,3,3,4,4-hexafluorocyclobuteneHFC-C1334cc cyclo-CF₂CF₂CH═CH— 3,3,4,4-tetrafluorocyclobutene HFC-C1436cyclo-CF₂CF₂CF₂CH═CH— 3,3,4,4,5,5,-hexafluorocyclopentene HFC-C1418ycyclo-CF₂CF═CFCF₂CF₂— 1,2,3,3,4,4,5,5-octafluorocyclopentene FC-C151-10ycyclo-CF₂CF═CFCF₂CF₂CF₂— 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene

The compounds listed in Table 2 are available commercially or may beprepared by processes known in the art or as described herein.

1,1,1,4,4-pentafluoro-2-butene may be prepared from1,1,1,2,4,4-hexafluorobutane (CHF₂CH₂CHFCF₃) by dehydrofluorination oversolid KOH in the vapor phase at room temperature. The synthesis of1,1,1,2,4,4-hexafluorobutane is described in U.S. Pat. No. 6,066,768,incorporated herein by reference.

1,1,1,4,4,4-hexafluoro-2-butene may be prepared from1,1,1,4,4,4-hexafluoro-2-iodobutane (CF₃CHICH₂CF₃) by reaction with KOHusing a phase transfer catalyst at about 60° C. The synthesis of1,1,1,4,4,4-hexafluoro-2-iodobutane may be carried out by reaction ofperfluoromethyl iodide (CF₃I) and 3,3,3-trifluoropropene (CF₃CH═CH₂) atabout 200° C. under autogenous pressure for about 8 hours.

3,4,4,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorinationof 1,1,1,2,2,3,3-heptafluoropentane (CF₃CF₂CF₂CH₂CH₃) using solid KOH orover a carbon catalyst at 200-300° C. 1,1,1,2,2,3,3-heptafluoropentanemay be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene(CF₃CF₂CF₂CH═CH₂).

1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,3,3,4-heptafluorobutane (CH₂FCF₂CHFCF₃) using solid KOH.

1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,2,4,4-heptafluorobutane (CHF₂CH₂CF₂CF₃) using solid KOH.

1,1,1,3,4,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,3,3,4,4-heptafluorobutane (CF₃CH₂CF₂CHF₂) using solid KOH.

1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,2,2,3-hexafluorobutane (CH₂FCH₂CF₂CF₃) using solid KOH.

1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4-hexafluorobutane (CF₃CH₂CF₂CH₂F) using solid KOH.

1,1,1,3-tetrafluoro-2-butene may be prepared by reacting1,1,1,3,3-pentafluorobutane (CF₃CH₂CF₂CH₃) with aqueous KOH at 120° C.

1,1,1,4,4,5,5,5-octafluoro-2-pentene may be prepared from(CF₃CHICH₂CF₂CF₃) by reaction with KOH using a phase transfer catalystat about 60° C. The synthesis of4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out by reactionof perfluoroethyliodide (CF₃CF₂I) and 3,3,3-trifluoropropene at about200° C. under autogenous pressure for about 8 hours.

1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF₃CF₂CHICH₂CF₂CF₃) byreaction with KOH using a phase transfer catalyst at about 60° C. Thesynthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane may be carriedout by reaction of perfluoroethyliodide (CF₃CF₂I) and3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂) at about 200° C. underautogenous pressure for about 8 hours.

1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be preparedby the dehydrofluorination of1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane(CF₃CHICH₂CF(CF₃)₂) with KOH in isopropanol. CF₃CHICH₂CF(CF₃)₂ is madefrom reaction of (CF₃)₂CFI with CF₃CH═CH₂ at high temperature, such asabout 200° C.

1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reactionof 1,1,1,4,4,4-hexafluoro-2-butene (CF₃CH═CHCF₃) withtetrafluoroethylene (CF₂═CF₂) and antimony pentafluoride (SbF₅).

2,3,3,4,4-pentafluoro-1-butene may be prepared by dehydrofluorination of1,1,2,2,3,3-hexafluorobutane over fluorided alumina at elevatedtemperature.

2,3,3,4,4,5,5,5-ocatafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solidKOH.

1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane overfluorided alumina at elevated temperature.

Many of the compounds of Formula I, Table 1 and Table 2 exist asdifferent configurational isomers or stereoisomers. When the specificisomer is not designated, the present invention is intended to includeall single configurational isomers, single stereoisomers, or anycombination thereof. For instance, F11E is meant to represent theE-isomer, Z-isomer, or any combination or mixture of both isomers in anyratio. As another example, HFC-1225ye is meant to represent theE-isomer, Z-isomer, or any combination or mixture of both isomers in anyratio.

The heat transfer fluid compositions of the present invention may begenerally useful when the fluoroolefin is present at about 1 weightpercent to about 99 weight percent, preferably about 20 weight percentto about 99 weight percent, more preferably about 40 weight percent toabout 99 weight percent and still more preferably 50 weight percent toabout 99 weight percent.

The present invention further provides compositions as listed in Table3.

TABLE 3 Concentration ranges (wt %) Most Components Preferred Morepreferred preferred HFC-1225ye/HFC-32 1-99/99-1 30-99/70-1 90-99/10-1;95/5/97/3 HFC-1225ye/HFC-134a 1-99/99-1 40-99/60-1 90/10 HFC-1225ye/CO₂0.1-99.9/99.9-0.1 70-99.7/30-0.3 99/1 HFC-1225ye/ammonia0.1-99.9/0.1-99.9 40-99.9/0.1-60 90/10, 85/15, 80/ 20, 95/5HFC-1225ye/HFC-1234yf 1-99/99-1 51-99/49-1 and 60/40, 51/49 60-90/40-10HFC-1225ye/HFC- 1-98/1-98/1-98 50-98/1-40/1-40 85/10/5 152a/HFC-3281/15/4 82/15/3 HFC-1225ye/HFC- 1-98/1-98/0.1-98 50-98/1-40/0.3-3084/15/1 152a/CO₂ 84/15.5/0.5 HFC-1225ye/HFC- 1-98/1-98/1-9850-98/1-40/1-20 85/13/2 152a/propane HFC-1225ye/HFC-152a/i-1-98/1-98/1-98 50-98/1-40/1-20 85/13/2 butane HFC-1225ye/HFC-1-98/1-98/1-98 50-98/1-40/1-20 85/13/2 152a/DME HFC-1225ye/HFC-1-98/1-98/1-98 20-90/1-50/1-60 152a/CF₃I HFC-1225ye/HFC- 1-98/1-98/1-9840-98/1-50/1-40 76/9/15 134a/HFC-152a HFC-1225ye/HFC- 1-98/1-98/1-981-80/1-80/1-80 88/9/3 134a/HFC-32 HFC-1225ye/HFC- 1-98/1-98/1-9840-98/1-50/1-20 86/10/4 134a/HFC-161 HFC-1225ye/HFC- 1-98/1-98/0.1-9840-98/1-50/0.3-30 88.5/11/0.5 134a/CO₂ HFC-1225ye/HFC- 1-98/1-98/1-9840-98/1-50/1-20 87/10/3 134a/propane HFC-1225ye/HFC-134a/i-1-98/1-98/1-98 40-98/1-50/1-20 87/10/3 butane HFC-1225ye/HFC-1-98/1-98/1-98 40-98/1-50/1-20 87/10/3 134a/DME HFC-1225ye/HFC-1-98/1-98/1-98 40-98/1-50/1-40 88/9/3 134/HFC-32 trans-HFC-1234ze/HFC-1-99/99-1 30-99/70-1 90/10 134a trans-HFC-1234ze/HFC-32 1-99/99-140-99/60-1 95/5 trans-HFC-1234ze/HFC- 1-98/1-98/1-98 20-90/0.1-60/1-7032/CF₃I trans-HFC-1234ze/HFC- 1-99/99-1 40-99/60-1 80/20 152atrans-HFC-1234ze/HFC-125 1-99/99-1 30-99/70-1 HFC-1234yf/HFC-134a1-99/99-1 30-99/70-1 90/10 HFC-1234yf/HFC-32 1-99/99-1 40-99/60-1 95/5HFC-1234yf/HFC-125 0.1-99/99-0.1 52-99/48-1 HFC-1234yf/HFC-152a1-99/99-1 40-99/60-1 80/20 HFC-1225ye/HFC- 1-97/1-97/1-97/20-97/1-80/1-50/ 74/8/17/1 134a/HFC-152a/HFC-32 0.1-97 0.1-50HFC-1225ye/HFC- 1-98/1-98/0.1-98 10-90/10-90/0.1-50 70/20/10 and1234yf/HFC-134a 20/70/10 HFC-1225ye/HFC- 1-98/1-98/0.1-9810-90/5-90/0.1-50 25/73/2, 1234yf/HFC-32 75/23/2, 49/49/2, 85/10/ 5,90/5/5 HFC-1225ye/HFC- 1-97/1-97/0.1-97/ 10-80/10-80/1-60/1234yf/HFC-32/CF₃I 1-97 1-60 HFC-1225ye/HFC- 1-98/1-98/0.1-9810-90/10-90/0.1-50 70/25/5 and 1234yf/HFC-152a 25/70/5 HFC-1225ye/HFC-1-98/1-98/0.1-98 10-90/10-90/0.1-50 25/71/4, 1234yf/HFC-125 75/21/4,75/24/1 and 25/74/1 HFC-1225ye/HFC-1234yf/ 1-98/1-98/1-98 9-90/9-90/1-6040/40/20 and CF₃I 45/45/10 HFC-32/HFC-125/HFC- 0.1-98/0.1-98/5-70/5-70/5-70 30/30/40 and 1225ye 0.1-98 23/25/52 HFC-32/HFC-125/trans-0.1-98/0.1-98/ 5-70/5-70/5-70 30/50/20 and HFC-1234ze 0.1-98 23/25/52HFC-32/HFC-125/HFC- 0.1-98/0.1-98/ 5-70/5-70/5-70 40/50/10, 1234yf0.1-98 23/25/52, 15/45/40, and 10/60/30 HFC-32/HFC-134a/HFC-1-97/1-97/1-97/ 1-60/1-60/1-60/ 1225ye/CF₃I 1-97 1-60HFC-32/HFC-134a/HFC- 1-96/1-96/1-96/ 1-50/1-50/1-50/1225ye/HFC-1234yf/CF₃I 1-96/1-96 1-50/1-50 HFC-32/HFC-125/HFC-1-96/1-96/1-96/ 1-50/1-50/1-50/ 134a/HFC-1225ye/CF₃I 1-96/1-96 1-50/1-50HFC-125/HFC-1225ye/n- 0.1-98/0.1-98/ 5-70/5-70/1-20 65/32/3 and butane0.1-98 85.1/11.5/3.4 HFC-32/NH₃/HFC-1225ye 1-98/1-98/1-981-60/10-60/10-90 HFC-32/NH₃/HFC- 1-97/1-97/1-97/ 1-60/1-60/10-80/1225ye/CF₃I 1-97 1-60 HFC-32/NH₃/HFC- 1-97/1-97/1-97/ 1-60/1-60/10-80/1234yf/CF₃I 1-97 5-80 HFC-125/trans-HFC- 0.1-98/0.1-98/ 5-70/5-70/1-2066/32/2 and 1234ze/n-butane 0.1-98 86.1/11.5/2.4 HFC-125/HFC-1234yf/n-0.1-98/0.1-98/ 5-70/5-70/1-20 67/32/1 and butane 0.1-98 87.1/11.5/1.4HFC-125/HFC- 0.1-98/0.1-98/ 5-70/5-70/1-20 85.1/11.5/3.41225ye/isobutane 0.1-98 and 65/32/3 HFC-1225ye/HFC- 0.1-98/0.1-98/20-98/1-60/0.1-40 125/ammonia 0.1-98 HFC-1225ye/HFC-32/HFC-0.1-97/0.1-97/ 20-97/1-60/1-60/ 125/ammonia 0.1-97/0.1-97 0.1-40HFC-125/trans-HFC- 0.1-98/0.1-98/ 5-70/5-70/1-20 86.1/11.5/2.41234ze/isobutane 0.1-98 and 66/32/2 HFC-125/HFC- 0.1-98/0.1-98/5-70/5-70/1-20 87.1/11.5/1.4 1234yf/isobutane 0.1-98 and 80-98/1-19/ and67/32/1 1-10 HFC-1234yf/HFC-32/HFC- 1-50/1-98/1-98 15-50/20-80/5-60 143aHFC-1234yf/HFC- 1-40/59-98/1-30 10-40/59-90/1-10 32/isobutaneHFC-1234yf/HFC-125/HFC- 1-60/1-98/1-98 10-60/20-70/20-70 143aHFC-1234yf/HFC- 1-40/59-98/1-20 10-40/59-90/1-10 125/isobutaneHFC-1234yf/HFC-125/CF₃I 1-98/0.1-98/1-98 10-80/1-60/1-60 HFC-1234yf/HFC-1-80/1-70/19-90 20-80/10-70/19-50 134/propane HFC-1234yf/HFC-134/DME1-70/1-98/29-98 20-70/10-70/29-50 HFC-1234yf/HFC- 1-80/1-80/19-9810-80/10-80/19-50 134a/propane HFC-1234yf/HFC-134a/n- 1-98/1-98/1-3010-80/10-80/1-20 butane HFC-1234yf/HFC- 1-98/1-98/1-30 10-80/10-80/1-20134a/isobutane HFC-1234yf/HFC- 1-98/1-98/1-40 10-80/10-80/1-20 134a/DMEHFC-1234yf/HFC-134a/CF₃I 1-98/1-98/1-98 10-80/1-60/1-60 HFC-1234yf/HFC-1-80/1-98/1-98 10-80/10-80/1-50 143a/propane HFC-1234yf/HFC-1-40/59-98/1-20 5-40/59-90/1-10 143a/DME HFC-1234yf/HFC-152a/n-1-98/1-98/1-30 10-80/10-80/1-20 butane HFC-1234yf/HFC- 1-98/1-90/1-4010-80/10-80/1-20 152a/isobutane HFC-1234yf/HFC- 1-70/1-98/1-9810-70/10-80/1-20 152a/DME HFC-1234yf/HFC-152a/CF₃I 1-98/1-98/1-9810-80/1-60/1-60 HFC-1234yf/HFC- 1-80/1-70/29-98 10-60/10-60/29-50227ea/propane HFC-1234yf/HFC-227ea/n- 40-98/1-59/1-20 50-98/10-49/1-10butane HFC-1234yf/HFC- 30-98/1-69/1-30 50-98/10-49/1-10 227ea/isobutaneHFC-1234yf/HFC- 1-98/1-80/1-98 10-80/10-80/1-20 227ea/DMEHFC-1234yf/n-butane/DME 1-98/1-40/1-98 10-80/10-40/1-20HFC-1234yf/isobutane/DME 1-98/1-50/1-98 10-90/1-40/1-20HFC-1234yf/DME/CF₃I 1-98/1-98/1-98 10-80/1-20/10-80HFC-1234yf/DME/CF₃SCF₃ 1-98/1-40/1-98 10-80/1-20/10-70HFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/10-80 1234ze/HFC-134HFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/10-80 1234ze/HFC-227eaHFC-1225ye/trans-HFC- 1-60/1-60/39-98 10-60/10-60/39-80 1234ze/propaneHFC-1225ye/trans-HFC- 1-98/1-98/1-30 10-80/10-80/1-20 1234ze/n-butaneHFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/1-30 1234ze/DMEHFC-1225ye/trans-HFC- 1-98/1-98/1-98 10-80/10-80/10-80 1234ze/CF₃SCF₃HFC-1225ye/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 1243zf/HFC-134HFC-1225ye/HFC-1243zf/n- 1-98/1-98/1-30 10-80/10-80/1-20 butaneHFC-1225ye/HFC- 1-98/1-98/1-40 10-80/10-80/1-30 1243zf/isobutaneHFC-1225ye/HFC- 1-98/1-98/1-98 10-80/10-80/1-30 1243zf/DMEHFC-1225ye/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 1243zf/CF₃IHFC-1225ye/HFC- 1-98/1-98/1-98 10-80/10-80/1-50 134/HFC-152aHFC-1225ye/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 134/HFC-227eaHFC-1225ye/HFC-134/n- 1-98/1-90/1-40 10-80/10-80/1-30 butaneHFC-1225ye/HFC- 1-98/1-90/1-40 10-80/10-80/1-30 134/isobutaneHFC-1225ye/HFC-134/DME 1-98/1-98/1-40 10-80/10-80/1-30 HFC-1225ye/HFC-40-98/1-59/1-30 50-98/1-49/1-20 227ea/DME HFC-1225ye/n-butane/DME1-98/1-30/1-98 60-98/1-20/1-20 HFC-1225ye/n- 1-98/1-20/1-9810-80/1-10/10-80 butane/CF₃SCF₃ HFC- 1-98/1-60/1-98 40-90/1-30/1-301225ye/isobutane/DME HFC-1225ye/isobutane/CF₃I 1-98/1-40/1-9810-80/1-30/10-80 trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/10-801243zf/HFC-227ea trans-HFC-1234ze/HFC- 1-98/1-98/1-30 10-80/10-80/1-201243zf/n-butane trans-HFC-1234ze/HFC- 1-98/1-98/1-40 10-80/10-80/1-301243zf/isobutane trans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-401243zf/DME trans-HFC-1234ze/HFC- 1-98/1-98/1-98 1-80/1-70/1-80 32/CF3Itrans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-50 134/HFC-152atrans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 134/HFC-227eatrans-HFC-1234ze/HFC- 1-98/1-98/1-40 10-80/10-80/1-30 134/DMEtrans-HFC-1234ze/HFC- 1-98/1-98/1-98 10-80/10-80/1-50 134a/HFC-152atrans-HFC-1234ze/HFC- 1-98/1-98/1-50 10-80/10-80/1-30 152a/n-butanetrans-HFC-1234ze/HFC- 1-98/1-98/1-98 20-90/1-50/1-30 152a/DMEtrans-HFC-1234ze/HFC- 1-98/1-98/1-40 10-80/10-80/1-30 227ea/n-butanetrans-HFC-1234ze/n- 1-98/1-40/1-98 10-90/1-30/1-30 butane/DMEtrans-HFC-1234ze/n- 1-98/1-30/1-98 10-80/1-20/10-80 butane/CF₃Itrans-HFC- 1-98/1-60/1-98 10-90/1-30/1-30 1234ze/isobutane/DMEtrans-HFC- 1-98/1-40/1-98 10-80/1-20/10-80 1234ze/isobutane/CF₃Itrans-HFC- 1-98/1-40/1-98 10-80/1-20/10-80 1234ze/isobutane/CF₃SCF₃HFC-1243zf/HFC-134/HFC- 1-98/1-98/1-98 10-80/10-80/10-80 227eaHFC-1243zf/HFC-134/n- 1-98/1-98/1-40 10-80/10-80/1-30 butaneHFC-1243zf/HFC-134/DME 1-98/1-98/1-98 10-80/10-80/1-30HFC-1243zf/HFC-134/CF₃I 1-98/1-98/1-98 10-80/10-80/10-80 HFC-1243zf/HFC-1-98/1-98/1-98 10-80/10-80/1-50 134a/HFC-152a HFC-1243zf/HFC-134a/n-1-98/1-98/1-40 10-80/10-80/1-30 butane HFC-1243zf/HFC- 1-70/1-70/29-9810-70/1-50/29-40 152a/propane HFC-1243zf/HFC-152a/n- 1-98/1-98/1-3010-80/1-80/1-20 butane HFC-1243zf/HFC- 1-98/1-98/1-40 10-80/1-80/1-30152a/isobutane HFC-1243zf/HFC- 1-98/1-98/1-98 10-80/1-80/1-30 152a/DMEHFC-1243zf/HFC-227ea/n- 1-98/1-98/1-40 10-80/1-80/1-30 butaneHFC-1243zf/HFC- 1-98/1-90/1-50 10-80/1-80/1-30 227ea/isobutaneHFC-1243zf/HFC- 1-98/1-80/1-90 10-80/1-80/1-30 227ea/DMEHFC-1243zf/n-butane/DME 1-98/1-40/1-98 10-90/1-30/1-30HFC-1243zf/isobutane/DME 1-98/1-60/1-98 10-90/1-30/1-30HFC-1243zf/isobutane/CF₃I 1-98/1-40/1-98 10-80/1-30/10-80HFC-1243zf/DME/CF₃SCF₃ 1-98/1-40/1-90 10-80/1-30/10-80HFC-1225ye/HFC-32/CF₃I 1-98/1-98/1-98 5-80/1-70/1-80 HFC-1225ye/HFC-1-97/1-97/1-97/ 1-80/1-70/5-70/ 1234yf/HFC-32/HFC-125 1-97 5-70HFC-1225ye/HFC- 1-97/1-97/1-97/ 5-80/5-70/5-70/ 1234yf/HFC-32/HFC-134a1-97 5-70 HFC-1225ye/HFC- 1-96/1-96/1-96/ 1-70/1-60/1-70/1234yf/HFC-32/HFC- 1-96/1-96 1-60/1-60 125/CF₃I HFC-1225ye/HFC-32/HFC-1-97/1-97/1-97/ 10-80/5-70/5-70/ 125/HFC-152a 1-97 5-70HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-70/5-70/ 125/isobutane1-97 1-30 HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-70/5-70/125/propane 1-50 1-30 HFC-1225ye/HFC-32/HFC- 1-97/1-97/1-97/5-70/5-70/5-70/ 125/DME 1-50 1-30 HFC-1225ye/HFC- 1-97/1-97/1-97/5-70/5-70/5-70/ 32/CF₃I/DME 1-50 1-30 HFC-1225ye/HFC-32/HFC-1-97/1-97/1-97/ 10-80/5-70/5-70/ 125/CF₃I 1-97 1-80HFC-1234yf/HFC-32/CF₃I 1-98/1-98/1-98 10-80/1-70/1-80HFC-1234yf/HFC-32/HFC- 1-97/1-97/1-97/ 5-70/5-80/1-70/ 134a/CF₃I 1-975-70 HFC-1234yf/HFC-32/HFC- 1-98/1-98/1-98 10-80/5-80/10-80 125HFC-1234yf/HFC-32/HFC- 1-97/1-97/1-97/ 10-80/5-70/10-80/ 125/CF3I 1-975-80

The most preferred compositions of the present invention listed in Table3 are generally expected to maintain the desired properties andfunctionality when the components are present in the concentrations aslisted +/−2 weight percent. The compositions containing CO₂ would beexpected to maintain the desired properties and functionality when theCO₂ was present at the listed concentration +/−0.2 weight percent.

The compositions of the present invention may be azeotropic ornear-azeotropic compositions. By azeotropic composition is meant aconstant-boiling mixture of two or more substances that behave as asingle substance. One way to characterize an azeotropic composition isthat the vapor produced by partial evaporation or distillation of theliquid has the same composition as the liquid from which it isevaporated or distilled, i.e., the mixture distills/refluxes withoutcompositional change. Constant-boiling compositions are characterized asazeotropic because they exhibit either a maximum or minimum boilingpoint, as compared with that of the non-azeotropic mixture of the samecompounds. An azeotropic composition will not fractionate within arefrigeration or air conditioning system during operation, which mayreduce efficiency of the system. Additionally, an azeotropic compositionwill not fractionate upon leakage from a refrigeration or airconditioning system. In the situation where one component of a mixtureis flammable, fractionation during leakage could lead to a flammablecomposition either within the system or outside of the system.

A near-azeotropic composition (also commonly referred to as an“azeotrope-like composition”) is a substantially constant boiling liquidadmixture of two or more substances that behaves essentially as a singlesubstance. One way to characterize a near-azeotropic composition is thatthe vapor produced by partial evaporation or distillation of the liquidhas substantially the same composition as the liquid from which it wasevaporated or distilled, that is, the admixture distills/refluxeswithout substantial composition change. Another way to characterize anear-azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially the same. Herein, a composition isnear-azeotropic if, after 50 weight percent of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed isless than about 10 percent.

Azeotropic compositions of the present invention at a specifiedtemperature are shown in Table 4.

TABLE 4 Wt % Wt % Component A Component B A B Psia kPa T(C.) HFC-1234yfHFC-32 7.4 92.6 49.2 339 −25 HFC-1234yf HFC-125 10.9 89.1 40.7 281 −25HFC-1234yf HFC-134a 70.4 29.6 18.4 127 −25 HFC-1234yf HFC-152a 91.0 9.017.9 123 −25 HFC-1234yf HFC-143a 17.3 82.7 39.5 272 −25 HFC-1234yfHFC-227ea 84.6 15.4 18.0 124 −25 HFC-1234yf propane 51.5 48.5 33.5 231−25 HFC-1234yf n-butane 98.1 1.9 17.9 123 −25 HFC-1234yf isobutane 88.111.9 19.0 131 −25 HFC-1234yf DME 53.5 46.5 13.1 90 −25 HFC-1225yetrans-HFC- 63.0 37.0 11.7 81 −25 1234ze HFC-1225ye HFC-1243zf 40.0 60.013.6 94 −25 HFC-1225ye HFC-134 52.2 47.8 12.8 88 −25 HFC-1225ye HFC-152a7.3 92.7 14.5 100 −25 HFC-1225ye propane 29.7 70.3 30.3 209 −25HFC-1225ye n-butane 89.5 10.5 12.3 85 −25 HFC-1225ye isobutane 79.3 20.713.9 96 −25 HFC-1225ye DME 82.1 17.9 10.8 74 −25 HFC-1225ye CF₃SCF₃ 37.063.0 12.4 85 −25 trans-HFC-1234ze HFC-1243zf 17.0 83.0 13.0 90 −25trans-HFC-1234ze HFC-134 45.7 54.3 12.5 86 −25 trans-HFC-1234ze HFC-134a9.5 90.5 15.5 107 −25 trans-HFC-1234ze HFC-152a 21.6 78.4 14.6 101 −25trans-HFC-1234ze HFC-227ea 59.2 40.8 11.7 81 −25 trans-HFC-1234zepropane 28.5 71.5 30.3 209 −25 trans-HFC-1234ze n-butane 88.6 11.4 11.982 −25 trans-HFC-1234ze isobutane 77.9 22.1 12.9 89 −25 trans-HFC-1234zeDME 84.1 15.9 10.8 74 −25 trans-HFC-1234ze CF₃SCF₃ 34.3 65.7 12.7 88 −25HFC-1243zf HFC-134 63.0 37.0 13.5 93 −25 HFC-1243zf HFC-134A 25.1 74.915.9 110 −25 HFC-1243zf HFC-152A 40.7 59.3 15.2 104 −25 HFC-1243zfHFC-227ea 78.5 21.5 13.1 90 −25 HFC-1243zf propane 32.8 67.2 31.0 213−25 HFC-1243zf n-butane 90.3 9.7 13.5 93 −25 HFC-1243zf isobutane 80.719.3 14.3 98 −25 HFC-1243zf DME 72.7 27.3 12.0 83 −25 cis-HFC-1234zeHFC-236ea 20.9 79.1 30.3 209 25 cis-HFC-1234ze HFC-245fa 76.2 23.8 26.1180 25 cis-HFC-1234ze n-butane 51.4 48.6 6.08 42 −25 cis-HFC-1234zeisobutane 26.2 73.8 8.74 60 −25 cis-HFC-1234ze 2-methylbutane 86.6 13.427.2 188 25 cis-HFC-1234ze n-pentane 92.9 7.1 26.2 181 25 HFC-1234yeHFC-236ea 24.0 76.0 3.35 23.1 −25 HFC-1234ye HFC-245fa 42.5 57.5 22.8157 25 HFC-1234ye n-butane 41.2 58.8 38.0 262 25 HFC-1234ye isobutane16.4 83.6 50.9 351 25 HFC-1234ye 2-methylbutane 80.3 19.7 23.1 159 25HFC-1234ye n-pentane 87.7 12.3 21.8 150 25

Additionally, ternary azeotropes composition have been found as listedin Table 5.

TABLE 5 Pres Pres Temp Component A Component B Component C Wt % A Wt % BWt % C (psi) (kPa) (° C.) HFC- HFC-32 HFC- 3.9 74.3 21.8 50.02 345 −251234yf 143A HFC- HFC-32 isobutane 1.1 92.1 6.8 50.05 345 −25 1234yf HFC-HFC-125 HFC- 14.4 43.5 42.1 38.62 266 −25 1234yf 143A HFC- HFC-125isobutane 9.7 89.1 1.2 40.81 281 −25 1234yf HFC- HFC-134 propane 4.339.1 56.7 34.30 236 −25 1234yf HFC- HFC-134 DME 15.2 67.0 17.8 10.3871.6 −25 1234yf HFC- HFC-134a propane 24.5 31.1 44.5 34.01 234 −251234yf HFC- HFC-134a n-butane 60.3 35.2 4.5 18.58 128 −25 1234yf HFC-HFC-134a isobutane 48.6 37.2 14.3 19.86 137 −25 1234yf HFC- HFC-134a DME24.0 67.9 8.1 17.21 119 −25 1234yf HFC- HFC-143a propane 17.7 71.0 11.340.42 279 −25 1234yf HFC- HFC-143a DME 5.7 93.0 1.3 39.08 269 −25 1234yfHFC- HFC-152a n-butane 86.6 10.8 2.7 17.97 124 −25 1234yf HFC- HFC-152aisobutane 75.3 11.8 12.9 19.12 132 −25 1234yf HFC- HFC-152a DME 24.643.3 32.1 11.78 81.2 −25 1234yf HFC- HFC- propane 35.6 17.8 46.7 33.84233 −25 1234yf 227ea HFC- HFC- n-butane 81.9 16.0 2.1 18.07 125 −251234yf 227ea HFC- HFC- isobutane 70.2 18.2 11.6 19.27 133 −25 1234yf227ea HFC- HFC- DME 28.3 55.6 16.1 15.02 104 −25 1234yf 227ea HFC-n-butane DME 48.9 4.6 46.4 13.15 90.7 −25 1234yf HFC- isobutane DME 31.226.2 42.6 14.19 97.8 −25 1234yf HFC- DME CF₃I 16.3 10.0 73.7 15.65 108−25 1234yf HFC- DME CF₃SCF₃ 34.3 10.5 55.2 14.57 100 −25 1234yf HFC-trans- HFC-134 47.4 5.6 47.0 12.77 88.0 −25 1225ye HFC- 1234ze HFC-trans- HFC- 28.4 52.6 19.0 11.63 80.2 −25 1225ye HFC- 227ea 1234ze HFC-trans- propane 20.9 9.1 70.0 30.36 209 −25 1225ye HFC- 1234ze HFC-trans- n-butane 65.8 24.1 10.1 12.39 85.4 −25 1225ye HFC- 1234ze HFC-trans- DME 41.0 40.1 18.9 10.98 75.7 −25 1225ye HFC- 1234ze HFC- trans-CF₃SCF₃ 1.0 33.7 65.2 12.66 87.3 −25 1225ye HFC- 1234ze HFC- HFC-HFC-134 28.7 47.3 24.1 13.80 95.1 −25 1225ye 1243zf HFC- HFC- n-butane37.5 55.0 7.5 13.95 96.2 −25 1225ye 1243zf HFC- HFC- isobutane 40.5 43.216.3 14.83 102 −25 1225ye 1243zf HFC- HFC- DME 19.1 51.0 29.9 12.15 83.8−25 1225ye 1243zf HFC- HFC- CF₃I 10.3 27.3 62.3 14.05 96.9 −25 1225ye1243zf HFC- HFC-134 HFC- 63.6 26.8 9.6 12.38 85.4 −25 1225ye 152a HFC-HFC-134 HFC- 1.3 52.3 46.4 12.32 84.9 −25 1225ye 227ea HFC- HFC-134n-butane 18.1 67.1 14.9 14.54 100 −25 1225ye HFC- HFC-134 isobutane 0.774.0 25.3 16.68 115 −25 1225ye HFC- HFC-134 DME 29.8 52.5 17.8 9.78 67.4−25 1225ye HFC- HFC- DME 63.1 31.0 5.8 10.93 75.4 −25 1225ye 227ea HFC-n-butane DME 66.0 13.0 21.1 11.34 78.2 −25 1225ye HFC- n-butane CF₃SCF₃71.3 5.6 23.0 12.25 84.5 −25 1225ye HFC- isobutane DME 49.9 29.7 20.412.83 88.5 −25 1225ye HFC- isobutane CF₃I 27.7 2.2 70.1 13.19 90.9 −251225ye Trans- HFC- HFC- 7.1 73.7 19.2 13.11 90.4 −25 HFC- 1243zf 227ea1234ze Trans- HFC- n-butane 9.5 81.2 9.3 13.48 92.9 −25 HFC- 1243zf1234ze Trans- HFC- isobutane 3.3 77.6 19.1 14.26 98.3 −25 HFC- 1243zf1234ze Trans- HFC- DME 2.6 70.0 27.4 12.03 82.9 −25 HFC- 1243zf 1234zeTrans- HFC-134 HFC- 52.0 42.9 5.1 12.37 85.3 −25 HFC- 152a 1234ze Trans-HFC-134 HFC- 30.0 43.2 26.8 12.61 86.9 −25 HFC- 227ea 1234ze Trans-HFC-134 DME 27.7 54.7 17.7 9.76 67.3 −25 HFC- 1234ze Trans- HFC-134aHFC- 14.4 34.7 51.0 14.42 99.4 −25 HFC- 152a 1234ze Trans- HFC-152an-butane 5.4 80.5 14.1 15.41 106 −25 HFC- 1234ze Trans- HFC-152a DME59.1 16.4 24.5 10.80 74.5 −25 HFC- 1234ze Trans- HFC- n-butane 40.1 48.511.3 12.61 86.9 −25 HFC- 227ea 1234ze Trans- n-butane DME 68.1 13.0 18.911.29 77.8 −25 HFC- 1234ze Trans- n-butane CF₃I 81.2 9.7 9.1 11.87 81.8−25 HFC- 1234ze Trans- isobutane DME 55.5 28.7 15.8 12.38 85.4 −25 HFC-1234ze Trans- isobutane CF₃I 34.9 6.1 59.0 12.57 86.7 −25 HFC- 1234zeTrans- isobutane CF₃SCF₃ 37.7 1.1 61.7 12.66 87.3 −25 HFC- 1234ze HFC-HFC-134 HFC- 58.6 34.1 7.3 13.54 93.4 −25 1243zf 227ea HFC- HFC-134n-butane 27.5 58.7 13.9 14.72 101 −25 1243zf HFC- HFC-134 DME 18.7 63.517.8 10.11 69.7 −25 1243zf HFC- HFC-134 CF₃I 11.4 23.9 64.7 14.45 99.6−25 1243zf HFC- HFC-134a HFC- 41.5 21.5 37.1 14.95 103 −25 1243zf 152aHFC- HFC-134A n-butane 7.0 81.4 11.6 17.03 117 −25 1243zf HFC- HFC-152apropane 2.9 34.0 63.0 31.73 219 −25 1243zf HFC- HFC-152a n-butane 28.860.3 11.0 15.71 108 −25 1243zf HFC- HFC-152a isobutane 6.2 68.5 25.317.05 118 −25 1243zf HFC- HFC-152a DME 33.1 36.8 30.1 11.41 78.7 −251243zf HFC- HFC- n-butane 62.0 28.4 9.6 13.67 94.3 −25 1243zf 227ea HFC-HFC- isobutane 27.9 51.0 21.1 15.00 103 −25 1243zf 227ea HFC- HFC- DME48.1 44.8 7.2 12.78 88.1 −25 1243zf 227ea HFC- n-butane DME 60.3 10.129.6 12.28 84.7 −25 1243zf HFC- isobutane DME 47.1 26.9 25.9 13.16 90.7−25 1243zf HFC- isobutane CF₃I 32.8 1.1 66.1 13.97 96.3 −25 1243zf HFC-DME CF₃SCF₃ 41.1 2.3 56.6 13.60 93.8 −25 1243zf

The near-azeotropic compositions of the present invention at a specifiedtemperature are listed in Table 6.

TABLE 6 Component A Component B (wt % A/wt % B) T(C.) HFC-1234yf HFC-321-57/99-43 −25 HFC-1234yf HFC-125 1-51/99-49 −25 HFC-1234yf HFC-1341-99/99-1 −25 HFC-1234yf HFC-134a 1-99/99-1 −25 HFC-1234yf HFC-152a1-99/99-1 −25 HFC-1234yf HFC-161 1-99/99-1 −25 HFC-1234yf HFC-143a1-60/99-40 −25 HFC-1234yf HFC-227ea 29-99/71-1 −25 HFC-1234yf HFC-236fa66-99/34-1 −25 HFC-1234yf HFC-1225ye 1-99/99-1 −25 HFC-1234yftrans-HFC-1234ze 1-99/99-1 −25 HFC-1234yf HFC-1243zf 1-99/99-1 −25HFC-1234yf propane 1-80/99-20 −25 HFC-1234yf n-butane 71-99/29-1 −25HFC-1234yf isobutane 60-99/40-1 −25 HFC-1234yf DME 1-99/99-1 −25HFC-1225ye trans-HFC-1234ze 1-99/99-1 −25 HFC-1225ye HFC-1243zf1-99/99-1 −25 HFC-1225ye HFC-134 1-99/99-1 −25 HFC-1225ye HFC-134a1-99/99-1 −25 HFC-1225ye HFC-152a 1-99/99-1 −25 HFC-1225ye HFC-1611-84/99-16, 90-99/ −25 10-1 HFC-1225ye HFC-227ea 1-99/99-1 −25HFC-1225ye HFC-236ea 57-99/43-1 −25 HFC-1225ye HFC-236fa 48-99/52-1 −25HFC-1225ye HFC-245fa 70-99/30-1 −25 HFC-1225ye propane 1-72/99-28 −25HFC-1225ye n-butane 65-99/35-1 −25 HFC-1225ye isobutane 50-99/50-1 −25HFC-1225ye DME 1-99/99-1 −25 HFC-1225ye CF₃I 1-99/99-1 −25 HFC-1225yeCF₃SCF₃ 1-99/99-1 −25 trans-HFC-1234ze cis-HFC-1234ze 73-99/27-1 −25trans-HFC-1234ze HFC-1243zf 1-99/99-1 −25 trans-HFC-1234ze HFC-1341-99/99-1 −25 trans-HFC-1234ze HFC-134a 1-99/99-1 −25 trans-HFC-1234zeHFC-152a 1-99/99-1 −25 trans-HFC-1234ze HFC-161 1-52/99-48, 87-99/ −2513-1 trans-HFC-1234ze HFC-227ea 1-99/99-1 −25 trans-HFC-1234ze HFC-236ea54-99/46-1 −25 trans-HFC-1234ze HFC-236fa 44-99/56-1 −25trans-HFC-1234ze HFC-245fa 67-99/33-1 −25 trans-HFC-1234ze propane1-71/99-29 −25 trans-HFC-1234ze n-butane 62-99/38-1 −25 trans-HFC-1234zeisobutane 39-99/61-1 −25 trans-HFC-1234ze DME 1-99/99-1 −25trans-HFC-1234ze CF₃SCF₃ 1-99/99-1 −25 trans-HFC-1234ze CF₃I 1-99/99-1−25 HFC-1243zf HFC-134 1-99/99-1 −25 HFC-1243zf HFC-134a 1-99/99-1 −25HFC-1243zf HFC-152a 1-99/99-1 −25 HFC-1243zf HFC-161 1-99/99-1 −25HFC-1243zf HFC-227ea 1-99/99-1 −25 HFC-1243zf HFC-236ea 53-99/47-1 −25HFC-1243zf HFC-236fa 49-99/51-1 −25 HFC-1243zf HFC-245fa 66-99/34-1 −25HFC-1243zf propane 1-71/99-29 −25 HFC-1243zf n-butane 62-99/38-1 −25HFC-1243zf isobutane 45-99/55-1 −25 HFC-1243zf DME 1-99/99-1 −25cis-HFC-1234ze HFC-236ea 1-99/99-1 25 cis-HFC-1234ze HFC-236fa 1-99/99-125 cis-HFC-1234ze HFC-245fa 1-99/99-1 25 cis-HFC-1234ze n-butane1-80/99-20 −25 cis-HFC-1234ze isobutane 1-69/99-31 −25 cis-HFC-1234ze2-methylbutane 60-99/40-1 25 cis-HFC-1234ze n-pentane 63-99/37-1 25HFC-1234ye HFC-134 38-99/62-1 25 HFC-1234ye HFC-236ea 1-99/99-1 −25HFC-1234ye HFC-236fa 1-99/99-1 25 HFC-1234ye HFC-245fa 1-99/99-1 25HFC-1234ye Cis-HFC-1234ze 1-99/99-1 25 HFC-1234ye n-butane 1-78/99-22 25HFC-1234ye cyclopentane 70-99/30-1 25 HFC-1234ye isobutane 1-68/99-32 25HFC-1234ye 2-methylbutane 47-99/53-1 25 HFC-1234ye n-pentane 57-99/43-125

Ternary and higher order near-azeotrope compositions comprisingfluoroolefins have also been identified as listed in Table 7.

TABLE 7 Near-azeotrope range Temp Components (weight percent) (° C.)HFC-1225ye/HFC-134a/HFC-152a 1-98/1-98/1-98 25HFC-1225ye/HFC-134a/HFC-161 1-98/1-98/1-98 25HFC-1225ye/HFC-134a/isobutane 1-98/1-98/1-40 25 HFC-1225ye/HFC-134a/DME1-98/1-98/1-20 25 HFC-1225ye/HFC-152a/isobutane 1-98/1-98/1-50 25HFC-1225ye/HFC-152a/DME 1-98/1-98/1-98 25 HFC-1225ye/HFC-1234yf/HFC-134a1-98/1-98/1-98 25 HFC-1225ye/HFC-1234yf/HFC-152a 1-98/1-98/1-98 25HFC-1225ye/HFC-1234yf/HFC-125 1-98/1-98/1-20 25HFC-1225ye/HFC-1234yf/CF₃I 1-98/1-98/1-98 25 HFC-1225ye/HFC-134a/HFC-1-97/1-97/1-97/1-10 25 152a/HFC-32 HFC-125/HFC-1225ye/isobutane80-98/1-19/1-10 25 HFC-125/trans-HFC- 80-98/1-19/1-10 251234ze/isobutane HFC-125/HFC-1234yf/isobutane 80-98/1-19/1-10 25HFC-32/HFC-125/HFC-1225ye 1-98/1-98/1-4 25HFC-32/HFC-125/trans-HFC-1234ze 1-98/1-98/1-50 25HFC-32/HFC-125/HFC-1234yf 1-98/1-98/1-55 25HFC-125/trans-HFC-1234ze/n-butane 80-98/1-19/1-10 25HFC-125/HFC-1234yf/n-butane 80-98/1-19/1-10 25HFC-1234yf/HFC-32/HFC-143a 1-50/1-98/1-98 −25HFC-1234yf/HFC-32/isobutane 1-40/59-98/1-30 −25HFC-1234yf/HFC-125/HFC-143a 1-60/1-98/1-98 −25HFC-1234yf/HFC-125/isobutane 1-40/59-98/1-20 −25HFC-1234yf/HFC-134/propane 1-80/1-70/19-90 −25 HFC-1234yf/HFC-134/DME1-70/1-98/29-98 −25 HFC-1234yf/HFC-134a/propane 1-80/1-80/19-98 −25HFC-1234yf/HFC-134a/n-butane 1-98/1-98/1-30 −25HFC-1234yf/HFC-134a/isobutane 1-98/1-98/1-30 −25 HFC-1234yf/HFC-134a/DME1-98/1-98/1-40 −25 HFC-1234yf/HFC-143a/propane 1-80/1-98/1-98 −25HFC-1234yf/HFC-143a/DME 1-40/59-98/1-20 −25 HFC-1234yf/HFC-152a/n-butane1-98/1-98/1-30 −25 HFC-1234yf/HFC-152a/isobutane 1-98/1-90/1-40 −25HFC-1234yf/HFC-152a/DME 1-70/1-98/1-98 −25 HFC-1234yf/HFC-227ea/propane1-80/1-70/29-98 −25 HFC-1234yf/HFC-227ea/n-butane 40-98/1-59/1-20 −25HFC-1234yf/HFC-227ea/isobutane 30-98/1-69/1-30 −25HFC-1234yf/HFC-227ea/DME 1-98/1-80/1-98 −25 HFC-1234yf/n-butane/DME1-98/1-40/1-98 −25 HFC-1234yf/isobutane/DME 1-98/1-50/1-98 −25HFC-1234yf/DME/CF₃I 1-98/1-98/1-98 −25 HFC-1234yf/DME/CF₃SCF₃1-98/1-40/1-80 −25 HFC-1225ye/trans-HFC- 1-98/1-98/1-98 −251234ze/HFC-134 HFC-1225ye/trans-HFC- 1-98/1-98/1-98 −25 1234ze/HFC-227eaHFC-1225ye/trans-HFC- 1-60/1-60/1-98 −25 1234ze/propaneHFC-1225ye/trans-HFC-1234ze/n- 1-98/1-98/1-30 −25 butaneHFC-1225ye/trans-HFC-1234ze/DME 1-98/1-98/1-98 −25HFC-1225ye/trans-HFC-1234ze/ 1-98/1-98/1-98 −25 CF₃SCF₃HFC-1225ye/HFC-1243zf/HFC-134 1-98/1-98/1-98 −25HFC-1225ye/HFC-1243zf/n-butane 1-98/1-98/1-30 −25HFC-1225ye/HFC-1243zf/isobutane 1-98/1-98/1-40 −25HFC-1225ye/HFC-1243zf/DME 1-98/1-98/1-98 −25 HFC-1225ye/HFC-1243zf/CF₃I1-98/1-98/1-98 −25 HFC-1225ye/HFC-134/HFC-152a 1-98/1-98/1-98 −25HFC-1225ye/HFC-134/HFC-227ea 1-98/1-98/1-98 −25HFC-1225ye/HFC-134/n-butane 1-98/1-90/1-40 −25HFC-1225ye/HFC-134/isobutane 1-98/1-90/1-40 −25 HFC-1225ye/HFC-134/DME1-98/1-98/1-40 −25 HFC-1225ye/HFC-227ea/DME 40-98/1-59/1-30 −25HFC-1225ye/n-butane/DME 1-98/1-30/1-98 −25 HFC-1225ye/n-butane/CF₃SCF₃1-98/1-20/1-98 −25 HFC-1225ye/isobutane/DME 1-98/1-60/1-98 −25HFC-1225ye/isobutane/CF₃I 1-98/1-40/1-98 −25trans-HFC-1234ze/HFC-1243zf/HFC- 1-98/1-98/1-98 −25 227eatrans-HFC-1234ze/HFC-1243zf/n- 1-98/1-98/1-30 −25 butanetrans-HFC-1234ze/HFC- 1-98/1-98/1-40 −25 1243zf/isobutanetrans-HFC-1234ze/HFC-1243zf/DME 1-98/1-98/1-98 −25trans-HFC-1234ze/HFC-134/HFC- 1-98/1-98/1-98 −25 152atrans-HFC-1234ze/HFC-134/HFC- 1-98/1-98/1-98 −25 227eatrans-HFC-1234ze/HFC-134/DME 1-98/1-98/1-40 −25trans-HFC-1234ze/HFC-134a/HFC- 1-98/1-98/1-98 −25 152atrans-HFC-1234ze/HFC-152a/n- 1-98/1-98/1-50 −25 butanetrans-HFC-1234ze/HFC-152a/DME 1-98/1-98/1-98 −25trans-HFC-1234ze/HFC-227ea/n- 1-98/1-98/1-40 −25 butanetrans-HFC-1234ze/n-butane/DME 1-98/1-40/1-98 −25trans-HFC-1234ze/n-butane/CF₃I 1-98/1-30/1-98 −25trans-HFC-1234ze/isobutane/DME 1-98/1-60/1-98 −25trans-HFC-1234ze/isobutane/CF₃I 1-98/1-40/1-98 −25trans-HFC-1234ze/isobutane/ 1-98/1-40/1-98 −25 CF₃SCF₃HFC-1243zf/HFC-134/HFC-227ea 1-98/1-98/1-98 −25HFC-1243zf/HFC-134/n-butane 1-98/1-98/1-40 −25 HFC-1243zf/HFC-134/DME1-98/1-98/1-98 −25 HFC-1243zf/HFC-134/CF₃I 1-98/1-98/1-98 −25HFC-1243zf/HFC-134a/HFC-152a 1-98/1-98/1-98 −25HFC-1243zf/HFC-134a/n-butane 1-98/1-98/1-40 −25HFC-1243zf/HFC-152a/propane 1-70/1-70/29-98 −25HFC-1243zf/HFC-152a/n-butane 1-98/1-98/1-30 −25HFC-1243zf/HFC-152a/isobutane 1-98/1-98/1-40 −25 HFC-1243zf/HFC-152a/DME1-98/1-98/1-98 −25 HFC-1243zf/HFC-227ea/n-butane 1-98/1-98/1-40 −25HFC-1243zf/HFC-227ea/isobutane 1-98/1-90/1-50 −25HFC-1243zf/HFC-227ea/DME 1-98/1-80/1-90 −25 HFC-1243zf/n-butane/DME1-98/1-40/1-98 −25 HFC-1243zf/isobutane/DME 1-98/1-60/1-98 −25HFC-1243zf/isobutane/CF₃I 1-98/1-40/1-98 −25 HFC-1243zf/DME/CF₃SCF₃1-98/1-40/1-90 −25

Additional compositions comprising fluoroolefins as disclosed in U.S.patent application Ser. No. 11/369,227 filed Mar. 2, 2006; U.S. patentapplication Ser. No. 11/393,109 filed Mar. 30, 2006; and U.S. patentapplication Ser. No. 11/486,791 filed Jul. 13, 2006; are intended to beincluded within the scope of the present invention.

Certain of the compositions of the present invention are non-azeotropiccompositions. Those compositions of the present invention falling withinthe preferred ranges of Table 3, but outside of the near-azeotropicranges of Table 6 and Table 7 may be considered to be non-azeotropic.

A non-azeotropic composition may have certain advantages over azeotropicor near azeotropic mixtures. A non-azeotropic composition is a mixtureof two or more substances that behaves as a mixture rather than a singlesubstance. One way to characterize a non-azeotropic composition is thatthe vapor produced by partial evaporation or distillation of the liquidhas a substantially different composition as the liquid from which itwas evaporated or distilled, that is, the admixture distills/refluxeswith substantial composition change. Another way to characterize anon-azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially different. Herein, a composition isnon-azeotropic if, after 50 weight percent of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed isgreater than about 10 percent.

The compositions of the present invention may be prepared by anyconvenient method to combine the desired amounts of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combine the components in an appropriate vessel.Agitation may be used, if desired.

An alternative means for making compositions of the present inventionmay be a method for making a refrigerant blend composition, wherein saidrefrigerant blend composition comprises a composition as disclosedherein, said method comprising (i) reclaiming a volume of one or morecomponents of a refrigerant composition from at least one refrigerantcontainer, (ii) removing impurities sufficiently to enable reuse of saidone or more of the reclaimed components, (iii) and optionally, combiningall or part of said reclaimed volume of components with at least oneadditional refrigerant composition or component.

A refrigerant container may be any container in which is stored arefrigerant blend composition that has been used in a refrigerationapparatus air-conditioning apparatus or heat pump apparatus. Saidrefrigerant container may be the refrigeration apparatus,air-conditioning apparatus or heat pump apparatus in which therefrigerant blend was used. Additionally, the refrigerant container maybe a storage container for collecting reclaimed refrigerant blendcomponents, including but not limited to pressurized gas cylinders.

Residual refrigerant means any amount of refrigerant blend orrefrigerant blend component that may be moved out of the refrigerantcontainer by any method known for transferring refrigerant blends orrefrigerant blend components.

Impurities may be any component that is in the refrigerant blend orrefrigerant blend component due to its use in a refrigeration apparatus,air-conditioning apparatus or heat pump apparatus. Such impuritiesinclude but are not limited to refrigeration lubricants, being thosedescribed earlier herein, particulates including but not limited tometal, metal salt or elastomer particles, that may have come out of therefrigeration apparatus, air-conditioning apparatus or heat pumpapparatus, and any other contaminants that may adversely effect theperformance of the refrigerant blend composition.

Such impurities may be removed sufficiently to allow reuse of therefrigerant blend or refrigerant blend component without adverselyeffecting the performance or equipment within which the refrigerantblend or refrigerant blend component will be used.

It may be necessary to provide additional refrigerant blend orrefrigerant blend component to the residual refrigerant blend orrefrigerant blend component in order to produce a composition that meetsthe specifications required for a given product. For instance, if arefrigerant blend has 3 components in a particular weight percentagerange, it may be necessary to add one or more of the components in agiven amount in order to restore the composition to within thespecification limits.

The heat transfer fluid compositions of the present invention will haveglobal warming potential (GWP) that are less than many hydrofluorocarbonrefrigerants currently in use. Preferably, such compositions will alsohave zero or low ozone depletion potential. One aspect of the presentinvention is to provide a refrigerant with a global warming potential ofless than 1000, less than 500, less than 150, less than 100, or lessthan 50. Another aspect of the present invention is to reduce the netGWP of refrigerant mixtures by adding fluoroolefins to said mixtures.

The compositions of the present invention may be useful as low globalwarming potential (GWP) replacements for currently used refrigerants,including but not limited to R134a (or HFC-134a1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane),R123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R11 (CFC-11,fluorotrichloromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa(or HFC-245fa, 1,1,1,3,3-pentafluoropropane), R114 (or CFC-114,1,2-dichloro-1,1,2,2-tetrafluoroethane), R236fa (or HFC-236fa,1,1,1,1,3,3,3-hexafluoropropane), R124 (or HCFC-124,2-chloro-1,1,1,2-tetrafluoroethane), R407C (ASHRAE designation for ablend of 52 weight percent R134a, 25 weight percent R125(pentafluoroethane), and 23 weight percent R32 (difluoromethane), R410A(ASHRAE designation for a blend of 50 weight percent R125 and 50 weightpercent R32), R417A, (ASHRAE designation for a blend of 46.6 weightpercent R125, 50.0 weight percent R134a, and 3.4 weight percentn-butane), R422A, R422B, R422C and R422D, (ASHRAE designation for ablend of 85.1 weight percent R125, 11.5 weight percent R134a, and 3.4weight percent isobutane), R404A, (ASHRAE designation for a blend of 44weight percent R125, 52 weight percent R143a (1,1,1-trifluoroethane),and 4.0 weight percent R134a) and R507A (ASHRAE designation for a blendof 50 weight percent R125 and 50 weight percent R143a). Additionally,the compositions of the present invention may be useful as replacementsfor R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designationfor a blend of 51.2 weight percent CFC-115 (chloropentafluoroethane) and48.8 weight percent HCFC-22).

Often replacement refrigerants are most useful if capable of being usedin the original refrigeration equipment designed for a differentrefrigerant. The compositions of the present invention may be useful asreplacements for the above-mentioned refrigerants in original equipment.Additionally, the compositions of the present invention may be useful asreplacements for the above mentioned refrigerants in equipment designedto use the above-mentioned refrigerants.

The compositions of the present invention may further comprise alubricant. Lubricants of the present invention comprise refrigerationlubricants, i.e. those lubricants suitable for use with refrigeration,air-conditioning, or heat pump apparatus. Among these lubricants arethose conventionally used in compression refrigeration apparatusutilizing chlorofluorocarbon refrigerants. Such lubricants and theirproperties are discussed in the 1990 ASHRAE Handbook, RefrigerationSystems and Applications, chapter 8, titled “Lubricants in RefrigerationSystems”, pages 8.1 through 8.21. Lubricants of the present inventionmay comprise those commonly known as “mineral oils” in the field ofcompression refrigeration lubrication. Mineral oils comprise paraffins(i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons),naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated,cyclic hydrocarbons containing one or more rings characterized byalternating double bonds). Lubricants of the present invention furthercomprise those commonly known as “synthetic oils” in the field ofcompression refrigeration lubrication. Synthetic oils comprisealkylaryls (i.e. linear and branched alkyl alkylbenzenes), syntheticparaffins and napthenes, and poly(alphaolefins). Representativeconventional lubricants of the present invention are the commerciallyavailable BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso®3GS and Suniso® 5GS (naphthenic mineral oil sold by Crompton Co.),Sontex® 372LT (naphthenic mineral oil sold by Pennzoil), Calumet® RO-30(naphthenic mineral oil sold by Calumet Lubricants), Zerol® 75, Zerol®150 and Zerol® 500 (linear alkylbenzenes sold by Shrieve Chemicals) andHAB 22 (branched alkylbenzene sold by Nippon Oil).

Lubricants of the present invention further comprise those that havebeen designed for use with hydrofluorocarbon refrigerants and aremiscible with refrigerants of the present invention under compressionrefrigeration, air-conditioning, or heat pump apparatus' operatingconditions. Such lubricants and their properties are discussed in“Synthetic Lubricants and High-Performance Fluids”, R. L. Shubkin,editor, Marcel Dekker, 1993. Such lubricants include, but are notlimited to, polyol esters (POEs) such as Castrol® 100 (Castrol, UnitedKingdom), polyalkylene glycols (PAGs) such as RL488A from Dow (DowChemical, Midland, Mich.), and polyvinyl ethers (PVEs). These lubricantsare readily available from various commercial sources.

Lubricants of the present invention are selected by considering a givencompressor's requirements and the environment to which the lubricantwill be exposed. Lubricants of the present invention preferably have akinematic viscosity of at least about 5 cs (centistokes) at 40° C.

Commonly used refrigeration system additives may optionally be added, asdesired, to compositions of the present invention in order to enhancelubricity and system stability. These additives are generally knownwithin the field of refrigeration compressor lubrication, and includeanti wear agents, extreme pressure lubricants, corrosion and oxidationinhibitors, metal surface deactivators, free radical scavengers, foamingand antifoam control agents, leak detectants and the like. In general,these additives are present only in small amounts relative to theoverall lubricant composition. They are typically used at concentrationsof from less than about 0.1% to as much as about 3% of each additive.These additives are selected on the basis of the individual systemrequirements. Some typical examples of such additives may include, butare not limited so to, lubrication enhancing additives, such as alkyl oraryl esters of phosphoric acid and of thiophosphates. Additionally, themetal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate orZDDP, Lubrizol 1375) and other members of this family of chemicals maybe used in compositions of the present invention. Other antiwearadditives include natural product oils and assymetrical polyhydroxyllubrication additives such as Synergol TMS (international Lubricants).Similarly, stabilizers such as anti oxidants, free radical scavengers,and water scavengers may be employed. Compounds in this category caninclude, but are not limited to, butylated hydroxy toluene (BHT) andepoxides.

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of an additive such as,for example, a stabilizer, free radical scavenger and/or antioxidant.Such additives include but are not limited to, nitromethane, hinderedphenols, hydroxylamines, thiols, phosphites, or lactones. Singleadditives or combinations may be used.

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of a water scavenger(drying compound). Such water scavengers may comprise ortho esters suchas trimethyl-, triethyl-, or tripropylortho formate.

In one embodiment, the present composition comprising a fluoroolefin mayfurther comprise at least one compound selected from the groupconsisting of: HFC-1225ye, HFC-1234ze, HFC-1234yf, HFC-1234ye,HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a,HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc,propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane,dimethylether, CF3SCF3, CO2, ammonia, and CF3I. These additionalcomponents are available commercially.

The fluoroolefin compositions of the present invention are more easilydetected at low levels as compared to the more conventional saturatedfluorocarbon working fluids by virtue of the double bond. Therefore,with the present invention, no tracer type compound such as a dye isneeded to detect the leakage, even at a low concentration level such aswould be produced by a small leak site.

In another embodiment, the present invention provides a method fordetecting a leak in a refrigeration or air-conditioning system whereinthe fluid is a refrigerant composition comprising carbon dioxide, saidmethod comprising adding a small amount of fluoroolefin to saidrefrigerant composition. This inventive method makes it possible todetect a leak or carbon dioxide from the system even in the presence ofambient carbon dioxide in the air. The sensors of the present inventionwill respond to the fluoroolefin thus signaling that a leak is present.For the addition of fluoroolefin to be effective in the present methodfor detecting a leak of carbon dioxide, the fluoroolefin may be presentat less than about 1 weight percent. In another embodiment, thefluoroolefin may be present in the range of about 0.1 weight percent (or1000 ppm by weight) to about 0.01 weight percent (or 100 ppm by weight).

EXAMPLE Near-infrared Spectrum for Fluoroolefin

This example demonstrates that a NIR spectrum can be obtained for afluoroolefin as described herein. A sample of1,2,3,3,3-pentafluoropropene (HFC-1225ye) was analyzed with a VarianCary 500 UV/Vis/NIR spectrophotometer at ambient temperature. A 10millimeter sample cell was charged with HFC-1225ye to a pressure of 748torr on a vacuum line, having previously been evacuated. A backgroundspectrum of the same evacuated (<1 mTorr) cell was acquired andsubtracted from the sample spectrum. For both sample and background,points were acquired at 1 nanometer (nm) resolution and averaging 0.2seconds per point, with a spectral bandwidth of 4 nm; the detector andgrating changeover occurred at 800 nm and the UV source was activated at350 nm; and the spectrum was scanned from 2600 to 190 nm. FIG. 2 showsthe raw NIR spectral data for the HFC-1225ye sample. FIG. 3 shows thebackground NIR spectrum acquired for the evacuated sample cell. And FIG.4 shows the background subtracted NIR spectrum for HFC-1225ye. Thesedata verify that NIR spectra for fluoroolefins may be obtained thatprovide a unique fingerprint for detection of this class of compound.

1. A method for detecting a leak of a composition comprising afluoroolefin from a fluid system containing said composition, comprisingsensing the leaked fluoroolefin with a sensing means proximate thecomponents of the fluid system, wherein said sensing means uses a NIRsensor that uses a light-emitting diode as the source of near infraredradiation for detecting the double bond structure of the leakedfluoroolefin.
 2. The method of claim 1, wherein the sensing meanscomprises a hand-held device.
 3. The method of claim 1, wherein thefluid system is a cooling system of an automotive vehicle.
 4. The methodof claim 1, wherein the fluoroolefin comprises a compound having theformula E- or Z—R¹CH═CHR² (Formula I), wherein R¹ and R² are,independently, C₁ to C₆ perfluoroalkyl groups.
 5. The method of claim 4,wherein the R¹ and R² groups are CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂,CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃,CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, andC(CF₃)₂CF₂C₂F₅.
 6. The method of claim 1, wherein the fluoroolefincomprises a compound selected from the group consisting of CF₃CF═CHF,CF₃CH═CF₂, CHF₂CF═CF₂, CHF₂CF═CHF, CF₃CF═CH₂, CF₃CH═CHF, CH₂FCF═CF₂,CHF₂CH═CF₂, CHF₂CF═CHF, CHF₂CF═CH₂, CF₃CH═CH₂, CH₃CF═CF₂, CH₂FCH═CF₂,CH₂FCF═CHF, CHF₂CH═CHF, CF₃CF═CFCF₃, CF₃CF₂CF═CF₂, CF₃CF═CHCF₃,CHF═CFCF₂CF₃, CHF₂CF═CFCF₃, (CF₃)₂C═CHF, CF₂═CHCF₂CF₃, CF₂═CFCHFCF₃,CF₂═CFCF₂CHF₂, CF₃CF₂CF═CH₂, CF₃CH═CHCF₃, CHF═CHCF₂CF₃, CHF═CFCHFCF₃,CHF═CFCF₂CHF₂, CHF₂CF═CFCHF₂, CH₂FCF═CFCF₃, CHF₂CH═CFCF₃, CF₃CH═CFCHF₂,CF₂═CFCF₂CH₂F, CF₂═CFCHFCHF₂, CH₂═C(CF₃)₂, CH₂FCH═CFCF₃, CF₃CH═CFCH₂F,CF₃CF₂CH═CH₂, CHF₂CH═CHCF₃, CF₃CF═CFCH₃, CH₂═CFCF₂CHF₂, CHF₂CF═CHCHF₂,CH₃CF₂CF═CF₂, CH₂FCF═CFCHF₂, CH₂FCF₂CF═CF₂, CF₂═C(CF₃)(CH₃),CH₂═C(CHF₂)(CF₃), CH₂═CHCF₂CHF₂, CF₂═C(CHF₂)(CH₃), CHF═C(CF₃)(CH₃),CH₂═C(CHF₂)₂, CF₃CF═CHCH₃, CH₂═CFCHFCF₃, CHF═CFCH₂CF₃, CHF═CHCHFCF₃,CHF═CHCF₂CHF₂, CHF═CFCHFCHF₂, CH₃CF═CHCF₃, CF₃CF═CFC₂F₅,CF₂═CFCF₂CF₂CF₃, (CF₃)₂C═CHCF₃, CF₃CF═CHCF₂CF₃, CF₃CH═CFCF₂CF₃,CHF═CFCF₂CF₂CF₃, CF₂═CHCF₂CF₂CF₃, CF₂═CFCF₂CF₂CHF₂, CHF₂CF═CFCF₂CF₃,CF₃CF═CFCF₂CHF₂, CF₃CF═CFCHFCF₃, CHF═CFCF(CF₃)₂, CF₂═CFCH(CF₃)₂,CF₃CH═C(CF₃)₂, CF₂═CHCF(CF₃)₂, CH₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CHF₂,CH₂═C(CF₃)CF₂CF₃, CF₂═CHCH(CF₃)₂, CHF═CHCF(CF₃)₂, CF₂═C(CF₃)CH₂CF₃,CF₃CH═CHCF₂CF₃, (CF₃)₂CFCH═CH₂, CF₃CF₂CF₂CH═CH₂, CH₂═CFCF₂CF₂CHF₂,CF₂═CHCF₂CH₂CF₃, CF₃CF═C(CF₃)(CH₃), CH₂═CFCH(CF₃)₂, CHF═CHCH(CF₃)₂,CH₂FCH═C(CF₃)₂, CH₃CF═C(CF₃)₂, (CF₃)₂C═CHCH₃, C₂F₅CF═CHCH₃,CF₃C(CH₃)═CHCF₃, CH₂═CHCF₂CHFCF₃, CH₂═C(CF₃)CH₂CF₃,CF₃(CF₂)₃CF═CF₂,CF₃CF₂CF═CFCF₂CF₃, (CF₃)₂C═C(CF₃)₂, (CF₃)₂CFCF═CFCF₃, (CF₃)₂C═CHC₂F₅,(CF₃)₂CFCF═CHCF₃, CF₃CH═CHCF(CF₃)₂,CF₃CH═CHCF₂CF₂CF₃,CF₂CF₂CH═CHCF₂CF₃,CF₃CF₂CF₂CF₂CH═CH₂, CH₂═CHC(CF₃)₃,(CF₃)₂C═C(CH₃)(CF₃), H₂═CFCF₂CH(CF₃)₂,CF₃CF═C(CH₃)CF₂CF₃,CF₃CH═CHCH(CF₃)₂, C₂F₅CF₂CF═CHCH₃,CH₂═CHCF₂CF₂CF₂CHF₂,(CF₃)₂C═CHCF₂CH₃, CH₂═C(CF₃)CH₂C₂F₅,CF₃CF₂CF₂C(CH₃)═CH₂, CF₃CF₂CF₂CH═CHCH₃, CH₂═CHCH₂CF₂C₂F₅,CF₃CF₂CF═CFC₂H₅, CH₂═CHCH₂CF(CF₃)₂, CF₃CF═CHCH(CF₃)(CH₃),(CF₃)₂C═CFC₂H₅, CF₃CF═CFCF₂CF₂C₂F₅, CF₃CF₂CF═CFCF₂C₂F₅,CF₃CH═CFCF₂CF₂C₂F₅, CF₃CF═CHCF₂CF₂C₂F₅, CF₃CF₂CH═CFCF₂C₂F₅,CF₃CF₂CF═CHCF₂C₂F₅, cyclo-CF₂CF₂CF═CF—, cyclo-CF₂CF₂CH═CH—,cyclo-CF₂CF₂CF₂CH═CH—, cyclo-CF₂CF═CFCF₂CF₂—, andcyclo-CF₂CF═CFCF₂CF₂CF₂.
 7. The method of claims 1, wherein thecomposition comprising a fluoroolefin further comprises at least onecompound selected from the group consisting of: HFC-1225ye, HFC-1234ze,HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a,HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa,HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane,cyclopentane, dimethylether, CF₃SCF₃, CO₂, ammonia, and CF₃I.
 8. Amethod for detecting a leak of a refrigerant fluid comprising carbondioxide from a refrigeration or air-conditioning system containing saidrefrigerant fluid, comprising (a) adding a fluoroolefin to saidrefrigerant fluid; and (b) sensing the leaked fluoroolefin with asensing means proximate the components of the system, wherein saidsensing means uses a sensor for detecting the double bond structure ofthe fluoroolefin.
 9. A fluid system, comprising (a) a refrigeration orair conditioning system containing a refrigerant fluid comprising afluoroolefin and (b) a sensing means proximate the components of therefrigeration of air conditioning system for detecting a leak from saidrefrigeration or air conditioning system, wherein said sensing meansuses a NIR sensor that uses a light-emitting diode as the source of nearinfrared radiation for detecting the double bond structure of the leakedfluoroolefin.
 10. The fluid system of claim 9, wherein the sensing meanscomprises a wand tip.
 11. The method of claim 8 wherein the fluoroolefinis added at less than about 1 weight percent.
 12. The fluid system ofclaim 9 wherein (a) is the cooling system of an automotive vehicle. 13.The method of claim 1 wherein the sensor detects the double bondstructure by measuring the near-infrared spectrum of the leakedfluoroolefin.
 14. The method of claim 13 wherein the sensor is a NIRsensor that uses a light-emitting diode as the source of near infraredradiation for detecting the double bond structure of the leakedfluoroolefin.
 15. The method of claim 8, wherein the sensing meanscomprises a sensor selected from the group consisting of: infraredsensors, UV sensors, NIR sensors, ion mobility or plasma chromatographs,gas chromatography, refractometry, mass spectroscopy, high temperaturethick film sensors, thin film field effect sensors, pellistor sensors,Taguchi sensors and quartz microbalance sensors.